Additive composition for mortars, cements and joint compounds and cementitious compositions made therefrom

ABSTRACT

An additive composition for mortars, exterior insulation finish systems, self-leveling compounds and joint compounds is disclosed. The additive composition contains a nitrogen-containing polymer and a reactive agent capable of forming a crosslinking reaction with the nitrogen-containing polymer. Small amounts of the additive composition contained in a product cannot only increase one or more properties of the product but can also minimize the use of redispersible polymers in the product.

CLAIM FOR PRIORITY

This application is a continuation-in-part of U.S. patent applicationSer. No. 12/313,977, filed Nov. 26, 2008, of the same title, which wasbased upon U.S. Provisional Patent Application Ser. No. 60/991,492,filed Nov. 30, 2007, also of the same title. The priorities of U.S.patent application Ser. Nos. 12/313,977 and 60/991,492 are herebyclaimed and the disclosures incorporated herein by reference.

BACKGROUND

Cementitious materials can include various different types of cements,compounds, mortars, joint compounds, construction adhesives, and thelike. These products typically contain a binder and a filler. The bindermay comprise, for instance, a cement such as Portland cement or gypsum.The filler, on the other hand, may comprise a quartz sand or calciumcarbonate.

In addition to a binder and a filler, the compositions can also containvarious other additives. For instance, cellulose derivatives and othermaterials have been added to the cementitious compositions. Thecellulose derivatives are added in order to improve the workability ofthe composition, to increase the water-retention properties of thecomposition, and to increase the adhesiveness and the resistance tosliding. Increasing water retention, for instance, can prevent thecomposition from losing water prior to setting on highly absorbentsubstrates and allows for control of the open time and adjusting time.If the composition sets too quickly, the resulting composite may notdevelop the mechanical adhesion strength required to keep a tileadhesive attached on the adjacent surface as well as to prevent cracks,for example. Workability is also improved due to the lubricantproperties of the cellulose ethers. Cellulose derivatives may be usedwith or without a polyvinyl alcohol resin in cementitious tile adhesivecompositions; see Great Britain 1,490,783 of Griffith et al. and GreatBritain 1,225,755 of Vaughn et al., the disclosures of which areincorporated herein by reference. Latex and other resinous additives forcementitious compositions are also seen in the following references:European Patent Application Publication 0 649 823 which discloses theuse of polyvinyl alcohol and polyvinyl acetate; U.S. Pat. No. 7,294,194to Reddy et al. which discloses various latexes for preservingelasticity; and United States Patent Application Publication No.2001/0018881 of Futami et al. which advocates the use of melamine andsulfonic acid/formaldehyde condensates, naphthalene sulfonic acidcondensates and amide resins in cement.

Synthetic polymer additives for mortars are frequently supplied asredispersible powders or emulsions. The redispersible polymer maycomprise, for instance, an emulsion made out of polyvinyl acetatehomopolymer and copolymers stabilized with polyvinyl alcohol. Theredispersible polymer may improve workability, sag resistance,flexibility and tension strength under standard conditions, but alsoafter water immersion, heat aging and freeze-thaw cycles and so forth.Exemplary redispersible powders are described in European PatentApplication Publication No. 1 158 007 of Hara et al. and European PatentApplication Publication No. 0 873 978 of Hornamen et al., both of whichrelate to polyvinyl alcohol (PVOH) stabilized latexes. The disclosuresof EP 1 158 007 and EP 0 873 978 are incorporated herein by reference.

Although the incorporation of cellulose derivatives, redispersiblepolymers and other additives has provided many advances in the art, somedeficiencies still remain. For example, cellulose ethers when present inthe composition can cause a considerable delay in cement setting.Redispersible polymers, on the other hand, can be relatively expensive,thus adding cost to the final product.

In view of the above, a need currently exists for additives that canfurther improve the properties of a cementitious composition. Inparticular, a need exists for additives that can be used to control thewet properties and the mechanical properties of a cementitiouscomposition containing the additives. A need also exists for additivesthat can reduce or eliminate the amount of redispersible polymers in acementitious composition without adversely affecting the properties ofthe composition. This need is based on both the high cost ofredispersible powders, and the fact that high levels of redispersiblepowders can cause an imbalance in a cementitious composition. Forexample, redispersible powders can help impart flexibility; however theytypically can hinder properties like water resistance.

SUMMARY OF INVENTION

In general, the present invention is directed to an additive compositionfor cementitious compositions and to cementitious compositions madetherefrom. Cementitious compositions may include, for instance, amortar, a cement, a joint compound, exterior insulation finishingsystems, self leveling systems and the like. Specific applicationsinclude: tile adhesives (bathroom & kitchen floor, countertop and wall);exterior insulation finishing systems (EIFS) (adhesive system forexterior wall insulation); self-leveling compounds (mortars that arepoured onto a floor for leveling and tile or carpet sub-surface);coatings; concrete repair; facade coatings; grouts; gypsum applications;joint fillers; mineral plasters; patch and repair mortars; renderingplaster; powder paints; sealing slurries; thin bed mortars; andtroweling compounds. In one embodiment, the cementitious composition canbe packaged in a dry form. In this embodiment, water can be added priorto use.

In one embodiment, the additive composition of the present inventioncomprises a nitrogen-containing polymer and a reactive agent capable offorming a cross-linking reaction with the nitrogen-containing polymer.The additive composition may, optionally, contain one or more additionalingredients such as, for instance a cellulose derivative and a polyvinylalcohol polymer. According to one embodiment, the nitrogen-containingpolymer may be a copolymer of a vinyl alcohol and a vinyl amine. Thereactive agent, in addition to being capable of forming a crosslinkingreaction with the nitrogen-containing polymer, can for instance, also becapable of forming a crosslinking reaction with the cellulosederivative, and/or the polyvinyl alcohol. In another embodiment, forinstance, the reactive agent may comprise a glyoxal, borax, or maleicanhydride copolymer, materials that are believed to form a crosslinkingreaction with the nitrogen-containing polymer and, optionally, with thecellulose derivative and/or the polyvinyl alcohol. Other crosslinkingagents that may be used include gluteraldehyde,succinic dialdehyde,blocked glyoxal(12% glyoxal, 33% dipropylene glycol,and water), cationicamine polymer-epichlorohydrin, polyamide epichlorohydrin, potassiumzirconium carbonate, ammonium zirconium carbonate, ketone formaldehyde,styrene maleic anhydride copolymer, cyclic amide condensate, and thelike.

The nitrogen-containing polymer is further described as a polymercontaining primary or secondary nitrogen functional groups, such asamines, imines, amides, and the like. For instance, in variousembodiments, the nitrogen-containing polymer comprisespolyvinylalcohol-co-vinylamine, polyvinylalcohol-co-vinylformamide,polyvinylamine, polyvinylformamide, polyethyleneamine,polyethyleneimine, polyacrylamide, or mixtures thereof. Suitablenitrogenous polymers may thus include any one or a combination of thefollowing nitrogen functionalities: primary amino (—NH₂) groups;mono-substituted (secondary) amino groups —NHR where R is hydrocarbyl,generally either alkyl or aryl, e.g., lower alkyl or phenyl, forexample, methylamino, ethylamino, isopropylamino, butylamino,cyclopropylamino, cyclohexylamino, n-hexylamino, phenylamino,benzylamino, chloroethylamino, hydroxyethylamino, etc.); amides—(CO)—NR¹ R²where R¹ and R² may be the same or different and are eitherhydrogen or R, wherein R is as defined above (including, for example,amides wherein one of R¹ or R² is H and the other is methyl, butyl,benzyl, etc.); imines and so forth. Typical nitrogen-containing polymersmay be prepared using one or more of the following classes of monomers:vinylamines; vinylformamides; ethyleneamines; ethyleneimines;acrylamides; methacrylamides; acrylates and methacrylates substitutedwith a primary or secondary amino group optionally bound through a loweralkylene linker (e.g., aminoethyl methacrylate); caprolactams and soforth. The foregoing list is intended to be illustrative and notlimiting with regard to possible nitrogen-containing monomers that canbe used in the preparation of suitable nitrogen-containing polymers foruse with the inventive additive compositions.

The derivatized cellulose that may be contained within the additivecomposition can be any suitable cellulose ether. For instance, in oneembodiment, the derivatized cellulose comprises methyl cellulose,hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethylcellulose, hydroxypropyl cellulose, ethyl cellulose, or mixturesthereof.

As mentioned, the nitrogen-containing polymer may, according to anembodiment be a vinyl alcohol and vinyl amine copolymer which, ifpresent can contain from about 2 to about 30 mole percent vinyl aminefunctionality. For instance, the vinyl alcohol and vinyl amine copolymermay contain from about 2 mole percent to about 12 mole percent vinylamine. The weight ratio of nitrogen-containing polymer presenting thecementitious composition can vary depending upon the particularapplication and the desired result. In one embodiment, for instance, thepercent addition of the nitrogen-containing polymer in the cementitiouscomposition can be from about 0.01% to about 5%, or more preferably 0.1%to 2%.

In one embodiment, the reactive agent, such as a glyoxal, can bepre-reacted with a cellulose derivative, polyvinyl alcohol, or aninorganic compound such as clays, calcium carbonates, calcium oxides,and the like. This effectively creates a carrier system for the reactiveagent that would allow for easy incorporation of both wet and dryreactive agents with the nitrogen-containing polymer and the othercomponents of the cementitious composition, if present. The weight ratioof the reactive agent to the carrier, if present, can be from about0.001:1 to about 0.5:1, or more preferably 0.01:1 to about 0.1:1.

In another preferred aspect of the invention, the reactive agent ispre-reacted with a carrier such as cellulose in a reversible reaction.These components can be prepared or purchased, e.g., FQ grades ofBERMOCOLL™ resins available from Akzo Nobel as is discussed hereinafter.

The additive composition can be incorporated into numerous constructionadhesives. In one embodiment, for instance, the additive composition canbe contained in a dry cementitious composition. The cementitiouscomposition in addition to the additive composition can contain a binderand a filler. The binder, for instance, may comprise cement, gypsum, ormixtures thereof. The filler, on the other hand, may comprise calciumcarbonate particles, quartz sand, or mixtures thereof.

In one particular embodiment, the cementitious composition contains thebinder in an amount from about 20 parts to about 60 parts by weight andthe filler in an amount from about 40 parts to about 80 parts by weight.The nitrogen-containing polymer can be present in the composition in anamount from about 0.01 parts to about 5 parts by weight, preferably fromabout 0.01 parts to about 2 parts by weight. According to thoseembodiments where a cellulose derivative is present, it may be presentin the cementitious composition in an amount from about 0.01 parts toabout 3 parts by weight, preferably from about 0.1 to about 1 part byweight.

In one particular embodiment, the cementitious composition can furthercontain a redispersible polymer powder. The redispersible polymer powdermay comprise, for instance, polyvinyl acetate homopolymer andcopolymers, with or without an olefin such as ethylene that aredispersible in water. The powder may be stabilized with thenitrogen-containing polymer alone or in combination with polyvinylalcohol polymer. The redispersible polymer powder can be present in thecomposition in an amount from 0 to about 16 parts by weight. In oneembodiment, for instance, the redispersible polymer powder is present inan amount less than about 2 parts by weight.

In addition to a redispersible polymer, various other additives andingredients can be contained in the cementitious composition. Forinstance, in one embodiment, the cementitious composition optionally maycontain additives, such as lubricants, hydrophobic agents, fillers,pigments, setting accelerators, retardants or mixtures thereof. Forexample, suitable modifiers may include sodium stearate silicones,siloxanes and so forth.

In an alternative embodiment, the nitrogen-containing polymer may beincorporated into a redispersible polymer powder that is then added tothe cementitious composition optionally in conjunction with thederivatized cellulose and crosslinking agent. In this embodiment, forinstance, the redispersible polymer may comprise a powder as describedabove. The powder, for instance, may include a copolymer of vinylacetate and a comonomer. The comonomer, for instance, may comprise anolefin, a vinyl ester of a carboxylic acid, vinyl chloride, styrene, ormixtures thereof. Suitable olefins that may be used include, forinstance, ethylene or propylene. Vinyl esters of carboxylic acids, onthe other hand, may comprise vinyl esters of alpha-branchedmonocarboxylic acids such as a vinyl ester of versatic acid. Versaticacid is a branched carboxylic acid having ten carbon atoms. The abovecopolymer if present can be combined with the nitrogen-containingpolymer.

In one embodiment, for instance, the redispersible polymer powdercontaining the polyvinyl alcohol polymer may contain a vinyl acetate anda comonomer in a weight ratio of from about 60:40 to about 90:10, suchas at a weight ratio of about 80:20. The polyvinyl alcohol polymer,optionally in conjunction with the nitrogen-containing polymer, may becombined with the above copolymer in order to stabilize the powder whenformed into an emulsion. The redispersible polymer powder may contain,in one embodiment, the polyvinyl alcohol polymer particles and/or thenitrogen-containing polymer particles in an amount from about 4% toabout 18% by weight, such as in an amount of about 8% to about 12% byweight, based upon the total weight of the monomers present used to formthe copolymer. In addition to the vinyl acetate copolymer, the polyvinylalcohol polymer and the nitrogen-containing polymer, the redispersiblepolymer may further include a defoamer, an initiator, one or moresurfactants, a buffer, and any other suitable additives.

In one embodiment, for instance, the redispersible polymer powder may beincorporated into the cementitious composition in an amount from about0.5 parts to about 16 parts by weight, such as from about 1 part toabout 6 parts by weight.

Other features and aspects of the present disclosure are discussed ingreater detail below.

DETAILED DESCRIPTION

The invention is described in detail below with reference to numerousembodiments and examples. Such discussion is for purposes ofillustration only. Modifications to particular examples within thespirit and scope of the present invention, set forth in the appendedclaims, will be readily apparent to one of skill in the art.

Terminology used herein is given its ordinary meaning consistent withthe usage of such terms in the chemical and polymer arts. Unlessotherwise specified, the version of a test method applied is that ineffect as of Jan. 1, 2008. %, percent, and so forth refers to percent byweight on a dry basis unless the usage or context clearly indicatesotherwise. “Dry” means substantially dry, but not excluding that amountof residual moisture which is bound to or sorbed by the material atequilibrium with is ordinary surroundings.

When we refer to a molar equivalent ratio of the reactive moieties ofthe reactive agent to nitrogen in a nitrogen-containing polymer, we arereferring to the use of a pair of reactive moieties capable ofcrosslinking. For example, 1 mol of glyoxal per mol of nitrogen is a 1:1ratio. Likewise, for example, a 1:1 molar equivalent ratio refers to 1mole of maleic anhydride units in a styrene maleic anhydride copolymerto 1 mole of nitrogen in the nitrogen-containing polymer in thecomposition. Zirconium is in a 1:1 molar equivalent ratio with thenitrogen in the nitrogen-containing polymer as a reactive agent whenpresent in equimolar amounts and so forth.

“PPHC” refers to parts per hundred weight of inorganic binder and fillerin a cementitious composition on a dry basis. For example, in acomposition containing 60 parts sand, 40 parts Portland Cement and 10parts polymer additive and water, the composition has 60 PPHC sand, 40PPHC binder and 10 PPHC polymer irrespective of the amount of wateradded.

In general, the present disclosure is directed to an additivecomposition that is well suited for use in cementitious compositions.For example, the additive composition can be included in variousproducts including a mortar, a cement, a joint compound, and the like.Cementitious compositions made in accordance with the present disclosuregenerally contain a binder and a filler. The binder may comprise, forinstance, a cement, such as Portland cement, and/or gypsum. Theseproducts can be packaged in dry form. When packaged in dry form, thecementitious composition may then be combined with water and mixed toform a slurry or paste. The wetted material is then applied to a desiredarea where it hardens over time. The additive composition of the presentdisclosure can be added to the cementitious composition to provide oneor more benefits and advantages.

The additive composition, for instance, has been found, in someapplications, to improve one or more properties of the cementitiouscomposition. The additive composition has also been found, in certainembodiments, to improve the properties of the resulting cement or mortarproduct, such as slip and water resistance in tile adhesive. As will bedescribed in greater detail below, use of the additive composition in acementitious composition can, in one particular embodiment, alsominimize the amount of redispersible polymers contained in thecomposition without adversely impacting upon the properties of theresulting product.

In general, the additive composition of the present disclosurecomprises: a nitrogen-containing polymer and a reactive agent capable offorming a cross-linking reaction with the nitrogen-containing polymer.In one embodiment the nitrogen-containing polymer may be a vinyl alcoholand vinyl amine copolymer. A reactive agent is selected that forms acrosslinking reaction with at least the nitrogen-containing polymer. Inone particular embodiment, for instance, the reactive agent may beconfigured to form a crosslinking reaction with two or more of the otheroptional components contained in the additive composition. Thenitrogen-containing polymer can be incorporated into a cementitouscomposition in accordance with the present disclosure either directlyor, alternatively, may be used to form a redispersible polymer that isthen added to the cementitious composition.

Cellulose derivatives that may optionally be included in the additivecomposition of the present disclosure include any suitable celluloseether. Cellulose ethers have been added to construction materials in thepast in order to increase the water retention capacity of the product,to increase the stability of the product under load, to improve theworking properties of the product prior to hardening, and/or to improvethe mechanical adhesion properties of the product.

Cellulose ethers that may be used according to the present disclosureinclude methyl cellulose, hydroxyethyl cellulose, hydroxypropylcellulose, carboxymethyl cellulose, ethyl hydroxyethyl cellulose,hydroxypropyl cellulose, ethyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methyl cellulose and mixtures thereof. In oneparticular embodiment, for instance, the cellulose ethers present withinthe additive composition include hydroxyethyl methyl cellulose,hydroxypropyl methyl cellulose, or mixtures thereof.

As described above, the nitrogen-containing polymer provided in theadditive composition may be a vinyl alcohol and vinyl amine copolymer.Processes for producing vinyl alcohol and vinyl amine copolymers aredisclosed, for instance, in U.S. Pat. No. 5,300,566, which isincorporated herein by reference. Vinyl alcohol and vinyl aminecopolymers, for instance, can be formed by copolymerizing vinyl acetateand an N-vinyl formamide to yield a poly(vinyl acetate)-co-poly(N-vinylformamide) which is thereafter hydrolyzed to form the copolymer. Thevinyl alcohol and vinyl amine copolymer can be described as having thefollowing structure:

wherein m is from about 0.80 to about 0.98 and n is from about 0.02 toabout 0.30.

As shown above, the vinyl alcohol and vinyl amine copolymer generallycontains from about 1 mole percent to about 30 mole percent vinyl aminefunctionality. For example, the vinyl alcohol and vinyl amine copolymercan contain vinyl amine in an amount from about 2 mole percent to about30 mole percent, such as from about 2 mole percent to about 12 molepercent. Vinyl alcohol and vinyl amine copolymers particularly wellsuited for use in the present disclosure can be obtained commerciallyfrom the Celanese Corporation of Dallas, Tex. Such copolymers arecommercially sold, for instance, under the trade name CELVOL®.

The various polymeric ingredients are of suitable molecular weight.Generally, polyvinyl alcohols, polyvinyl amines, and so forth useful inconnection with the invention have molecular weights (number average) inthe range of from 5,000-200,000 or so. For example, a suitable vinylamine nitrogen-containing polymer may have a number average molecularweight of from 35,000-40,000 Daltons/mol corresponding to a weightaverage molecular weight of 55,000-75,000 Daltons/mol or so. Cellulosederivatives typically have higher molecular weights; generally havingmolecular weights (number average) in excess of 100,000 Daltons/mol asis known in the art.

The addition of a nitrogen-containing polymer, which according to oneembodiment may be a vinyl alcohol and vinyl amine copolymer into acementitious composition can provide various advantages and benefits.For example, vinyl alcohol and vinyl amine containing copolymers haveenhanced cold water solubility, can improve the open time,adjustability, tensile and shear adhesion strength and compressivestrength, of a resulting composition, and can be used to better controlsetting times for the cement or mortar product, especially when combinedwith a reactive agent that is capable of forming a crosslinking reactionwith the nitrogen-containing polymer and other optional ingredients suchas a cellulose derivative.

The reactive agent present within the additive composition can be anysuitable reactive agent capable of crosslinking with thenitrogen-containing polymer. In one particular embodiment, for instance,the reactive agent may comprise a dialdehyde, such as a glyoxal orgluteraldehyde. A glyoxal or gluteraldehyde reactive agent, for example,is capable of reacting with the nitrogen-containing polymer and,optionally with the cellulose derivatives if present. A glyoxal whenreacted with a nitrogen-containing polymer may form, for instance, animine. In addition to a glyoxal or gluteraldehyde, various otherreactive agents may be used. For instance, other reactive agents thatmay be incorporated into the formulation include borax, succinicdialdehyde, blocked glyoxal (12% glyoxal, 33% dipropylene glycol, andwater), cationic amine polymer-epichlorohydrin, polyamideepichlorohydrin, potassium zirconium carbonate, ammonium zirconiumcarbonate, ketone formaldehyde, styrene maleic anhydride copolymer,cylic amide condensate, and the like.

When contained in a cementitious composition, the components of theadditive composition of the present disclosure may be added separatelyto the cementitious composition or can be first blended together andthen added. In one embodiment, the reactive agent can be pre-reactedwith a carrier prior to being incorporated into the cementitiouscomposition. The carrier can consist of a cellulose ether, polyvinylalcohol, starch, polyacrylamide, or other water soluble organiccompound. Furthermore, the carrier can also be inorganic in nature,specifically a clay, calcium carbonate, calcium oxide, and the like. Theamount of reactive agent contained within the additive composition candepend upon various factors and the desired result. In those embodimentswhere the carrier is present, the weight ratio of the carrier to thenitrogen-containing polymer can also vary depending upon the particularapplication. In one particular embodiment, for instance, the weightratio of the nitrogen-containing polymer to the carrier can be fromabout 1:5 to about 5:1. For instance, the weight ratio of thenitrogen-containing polymer to the cellulose derivative can be fromabout 1:4 to about 4:1. In those embodiments where the additiveadditionally contains the cellulose derivative and the polyvinyl alcoholpolymer the weight ratio of the cellulose derivative to the polyvinylalcohol polymer can also vary. In one particular embodiment, forinstance, the weight ratio of the polyvinyl alcohol polymer to thecellulose derivative can be from about 1:5 to about 5:1. For instance,the weight ratio of the polyvinyl alcohol polymer to the cellulosederivative can be from about 1:4 to about 4:1.

In one preferred aspect of the invention, the reactive agent ispre-reacted with a carrier such as cellulose in a reversible reaction.These components can be prepared or purchased, e.g., FQ grades ofBERMOCOLL™ resins available from Akzo Nobel. The FQ grades of BERMOCOLL™cellulose ethers are powders with delayed hydration which provideexceptional handling flexibility and control of solubilization rate.This delay of hydration has been achieved by reaction with glyoxalduring production. In the chemical reaction, the polymer chains of thecellulose ether become linked to the bifunctional aldehyde glyoxal,forming a hemi-acetal. Cellulose ethers, crosslinked in this manner,lose their capability to hydrate but they are readily wetted out by coldwater and will disperse uniformly without lumping, and with minimalagitation. In the acid pH range, and low temperature of the water,hemi-acetals are relatively stable. At higher pH values and temperaturesseen in cement applications, the crosslinkers are broken and thecellulose ethers dissolve spontaneously, releasing the glyoxal as areactive agent.

In those embodiments where the additive additionally contains thecellulose derivative and the polyvinyl alcohol polymer the weight ratioof the cellulose derivative to the polyvinyl alcohol polymer can alsovary. In one particular embodiment, for instance, the weight ratio ofthe polyvinyl alcohol polymer to the cellulose derivative can be fromabout 1:5 to about 5:1. For instance, the weight ratio of the polyvinylalcohol polymer to the cellulose derivative can be from about 1:4 toabout 4:1.

When incorporated into a mortar or cement product, the amount of theadditive composition present in the product can vary. In general,however, very small amounts of the additive composition can produce theintended benefits and advantages. For instance, in general, the additivecomposition can be present in a cementitious composition in an amountless than about 5% by weight, such as less than about 3% by weight, suchas even less than about 1% by weight, based upon the weight of thesolids present.

The additive composition of the present invention can be incorporatedinto numerous different types of adhesive and construction products.Products that can be formulated with the additive composition includemortars, cements and joint compounds. Particular products, for instance,that can be made with the additive composition include tile adhesives,exterior insulation and finishing system adhesives, trowelingcompositions, leveling compounds, grouts, reinforcing mortars forexterior insulation and finishing systems, wood flooring adhesives,cementing compositions useful in cementing oil, gas and water wells,patching mortars, joint fillers, plasters, and the like.

In one embodiment, for instance, the additive composition of the presentinvention may be incorporated into a cementitious composition containinga binder and a filler. The binder may comprise, for instance, anysuitable cement, such as Portland cement, gypsum, an aluminate, ormixtures thereof. The binder can be present in the cementitiouscomposition in an amount from about 5% to about 80% by weight, such asfrom about 20% to about 50% by weight. When describing the cementitiouscomposition, the above percentages by weight are based upon the weightpercentage of dry material and thus exclude water if present in theproduct.

In general, the cementitious composition may contain any suitablefiller. Fillers that may be used include, for instance, quartz sand,calcium carbonate such as limestone, talc, dolomite, aluminum silicates,mica, pumice, perlites, vermiculites, and mixtures thereof. Fillers canbe present in the cementitious composition in an amount from about 10%to about , 90% by weight, such as from about 40% to about 90% by weight,such as from about 60% to about 80% by weight.

As described above, the additive composition of the present inventionmay be present in the cementitious composition in relatively smallamounts. The nitrogen-containing polymer may be present in thecementitious composition in an amount from about 0.01% to about 5% byweight, such as from about 0.1% to about 1% by weight. Thenitrogen-containing polymer may be added to the cementitious compositioneither directly or in conjunction with the redispersible polymer powderas will be described in greater detail below. In one particularembodiment, for instance, the cellulose derivative may be present in thecomposition in an amount from about 0.1% to about 3% by weight, such asfrom about 0.3% to about 0.5% by weight. In yet another embodiment, thepolyvinyl alcohol polymer may be present in the cementitious compositionin an amount from about 0.05% to about 5% by weight, such as from about0.05% to about 2% by weight. The polyvinyl alcohol polymer may also beadded into the cementitious composition either directly and/or in/conjunction with the redispersible polymer powder.

In addition to the above ingredients, the cementitious composition maycontain various other components. For instance, in one embodiment, thecementitious composition may contain a water redispersible polymerpowder. Redispersible polymer powders are polymer powders which breakdown in water into primary particles, which are then dispersed in thewater.

Suitable redispersible polymers that may be used include, for instance,those based on one or more vinyl chlorides, styrenes, vinyl esters ofunbranched or branched alkylcarboxylic acids having from 1 to 15 carbonatoms, methacrylic esters and acrylic esters of alcohols having from 1to 10 carbon atoms, vinyl-aromatics, olefins, dienes, and vinyl halidesas monomers or comonomers. It is also possible to use mixtures of thesepolymers made using one or more of the above-described monomers.

Suitable vinyl esters include vinyl acetate, vinyl propionate, vinylbutyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate,vinyl pivalate, and vinyl esters of alpha-branched monocarboxylic acidshaving from 5 to 11 carbon atoms, examples being VeoVa5®, VeoVa9®,VeoVa10® or VeoVa11® which are commercially available from HexionSpecialty Chemicals. Suitable methacrylic esters or acrylic esters aremethyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate,n-butyl methacrylate, and 2-ethylhexyl acrylate. Suitablevinyl-aromatics are styrene, methylstyrene, and vinyltoluene. Oneexample of a vinyl halide is vinyl chloride. Suitable olefins areethylene and propylene, and suitable dienes are 1,3-butadiene andisoprene.

If desired, the polymers may also contain from 0.1 to 10% by weight,based on the overall weight of the polymer, of functional comonomerunits, for example ethylenically unsaturated monocarboxylic ordicarboxylic acids such as acrylic acid; ethylenically unsaturatedcarboxamides such as (meth)acrylamide; ethylenically unsaturatedsulfonic acids and/or their salts, preferably vinylsulfonic acid;polyethylenically unsaturated comonomers such as divinyl adipate,diallyl maleate, allyl methacrylate and triallyl cyanurate, and/orN-methylol(meth)acrylamides and their ethers, such as their isobutoxy orn-butoxy ethers.

Particular redispersible polymers that may be used include the followingwherein the weight percentages provided below add up to 100% by weight,together, where appropriate, with the fraction of functional comonomerunits.

From among the vinyl ester polymers: vinyl acetate polymers, vinylacetate-ethylene copolymers with an ethylene content of from 1 to 60% byweight; vinyl ester-ethylene-vinyl chloride copolymers with an ethylenecontent of from 1 to 40% by weight and a vinyl chloride content of from20 to 90% by weight; vinyl acetate copolymers with from 1 to 50% byweight of one or more copolymerizable vinyl esters such as vinyllaurate, vinyl pivalate, vinyl esters of an alpha-branched carboxylicacid, especially versatic acid vinyl esters, which may also contain from1 to 40% by weight of ethylene; and vinyl acetate-acrylic estercopolymers with from 1 to 60% by weight of acrylic ester, especiallymethyl methacrylate, n-butyl acrylate, or 2-ethylhexyl acrylate, whichmay also contain from 1 to 40% by weight of ethylene.

From among the (meth)acrylic ester polymers: polymers of n-butylacrylate or 2-ethylhexyl acrylate; copolymers of methyl methacrylatewith n-butyl acrylate and/or 2-ethylhexyl acrylate; and copolymers ofmethyl methacrylate with 1,3-butadiene.

From among the vinyl chloride polymers, besides the abovementioned vinylester/vinyl chloride/ethylene copolymers: vinyl chloride-ethylenecopolymers and vinyl chloride-acrylate copolymers.

Styrene polymers that may be used include: styrene-1,3-butadienecopolymers and styrene-acrylic ester copolymers such as styrene-n-butylacrylate or styrene-2-ethylhexyl acrylate copolymers, each with astyrene content of from 10 to 70% by weight. Other styrene polymers arestyrene-1,3-butadiene copolymers having a styrene content of from 10 to70% by weight and a 1,3-butadiene content of from 30 to 90% by weight,with or without the abovementioned functional comonomer units, thefractions in % by weight adding up to 100% by weight.

Aqueous polymer dispersions and the water-redispersible powders of theabovementioned polymers that are obtainable from them by drying areknown and are available commercially. The polymers are prepared in aconventional manner, preferably by an emulsion polymerization process.The dispersions used may be stabilized with an emulsifier or else with aprotective colloid, an example being polyvinyl alcohol.

Polyvinyl alcohols that may be used include those that are partially (orintermediate) hydrolyzed and have a degree of hydrolysis of from about80 to up to about 95 mole percent. Likewise, so called “fully”hydrolyzed polyvinyl alcohol having a degree of hydrolysis of more than95% can be used. The polyvinyl alcohol particles can be incorporatedinto the redispersible polymer in order to stabilize the composition.Polyvinyl alcohol can be incorporated into the redispersible polymercomposition, for instance, in an amount from about 4% to about 20% byweight. Greater amounts of polyvinyl alcohol powders may also be addedfor various other reasons. For instance, polyvinyl alcohol powders havebeen incorporated into cementitious compositions in order to improve theworkability of the composition when wet and also to improve mechanicaladhesion strength. In the past, redispersible polymer powders weretypically present in cementitious compositions in an amount of about0.5% to about 16% by weight.

Although redispersible polyvinyl alcohol powders can provide variousbenefits and advantages when incorporated into a cementitiouscomposition, unfortunately such redispersible polymers can significantlyaffect the cost of the final product, as well as altering the balance ofperformance in such a composition. For example, in a cementitious tileadhesive, high levels of redispersible powders impart good flexibility,freeze-thaw resistance, and resistance to heat aging; however, thosesame high levels of redispersible powder tend to negatively impactproperties like water immersion resistance and resistance to slip on ahorizontal surface.

In one embodiment of the present invention, by incorporating theadditive composition of the present invention into the cementitiouscomposition, the amount of redispersible polymer present in thecomposition can be drastically reduced or even negated without adverselyinterfering with the physical properties of the resulting product. Moreparticularly, cementitious compositions can be formulated in accordancewith the present disclosure that contain a redispersible polymer in anamount from 0% to about 16% by weight, such as less than about 2% byweight. For instance, in one embodiment, a redispersible polymer may bepresent in the cementitious composition in an amount less than about 1%by weight, such as less than about 0.5% by weight.

As will become apparent from the examples which follow, benefits seeninclude, for example, improved slip and water resistance in tileadhesives, as well as reduced cost.

In an alternative embodiment, the nitrogen-containing polymer can beincorporated into a redispersible polymer powder which is then added tothe cementitious composition. For example, in one embodiment, all or aportion of the polyvinyl alcohol contained in the redispersible polymercan be replaced with a nitrogen-containing polymer. Thus, aredispersible polymer composition can be formulated in accordance withthe present disclosure that contains a nitrogen-containing polymer in anamount from about 4% to about 20% by weight, such as in an amount fromabout 8% to about 14% by weight. Again, the nitrogen-containing polymercan be used alone or in conjunction with polyvinyl alcohol particles inthe redispersible polymer composition.

In addition to the above components, the cementitious composition cancontain various other ingredients and additives. For instance, thecementitious composition may also contain defoamers, dispersing aids,antioxidants, and the like. Antioxidants that may be contained in thecomposition include, for instance, one or more sterically hinderedphenol or hydroquinone, aromatic amine, organosulfur compound,phosphite, and phosphonite antioxidants.

Other additives that may be contained in the cementitious compositioninclude accelerators, retardants, standardizers, air pore formers, andnatural or synthetic polymer fibers.

In one embodiment, for instance, the composition may also contain alubricant, such as sodium stearate. The sodium stearate may be presentin an amount less than about 5% by weight, such as in an amount fromabout 0.1% to about 2% by weight.

Cementitious compositions made in accordance with the present inventionmay be formulated so that the compositions are easily workable whencombined with water, have good mechanical adhesive strength properties(as tensile, compressive and/or shear) and set properties in anappropriate amount of time.

The nitrogen-containing polymer improves a wide range of properties ofthe cementitious composition, especially the working properties of thecomposition and may also increase the tensile strength and mechanicaladhesion properties of the product. It is believed that the optionallypresent components of the additive composition may work synergisticallytogether with the nitrogen-containing polymer to improve the propertiesof a cementitious composition. For instance, inclusion of the cellulosederivative is believed to increase the water retention capacity of theresulting composition, increase the workability of the composition whencombined with water, and to improve the stability of the resultingproduct under load. The polyvinyl alcohol polymer is believed to improvethe working properties of a cementitious composition and, in someembodiments, to increase the tensile strength of the resulting product.The polyvinyl alcohol polymer may also improve the mechanical adhesionproperties of the product.

When a cementitious composition is combined with water, althoughunknown, it is believed that the reactive agent may undergo acrosslinking reaction with the nitrogen-containing polymer. Inparticular, when the cementitious composition is combined with water,the pH of the composition may be alkaline which may cause the reactiveagent, such as the glyoxal, to react with the nitrogen-containingpolymer. Nitrogen-containing polymers undergo relatively fastcrosslinking reactions. Thus, it is believed that the properties of thenitrogen-containing polymer, optionally combined with the othercomponents of the additive composition result in a better balance ofattributes that when mixed with the cementitious components results inenhanced properties. In addition, all of these improvements are realizedwhile also minimizing the amount of redispersible polymer present in thecomposition to achieve desired physical properties.

The present disclosure may be better understood with reference to thefollowing examples.

Examples

The following examples were conducted in order to demonstrate some ofthe advantages and benefits of the present disclosure.

The following test for cementitious tile adhesives were conducted in thefollowing examples and fall under the European Norm 12004:

-   Open time (minutes): EN 1346-   Tensile Strength @ 5 minutes and Tensile Strength @ 10 minutes-   (Nw/mm2): EN 1348-   Tensile Adhesion Strength after water immersion: EN 1348-   Tensile Strength after heat aging: EN 1348-   Tensile Strength after freeze-thaw cycles: EN 1348-   Deformation/Flexibility: EN 12002

Further cementitious tile adhesive tests were also conducted and testedunder Mexican Specifications:

-   Shear Resistance (kg/cm2): Test No. NMX-C-420 ONNCCE(2003)-   Compressive Strength (kg/cm2): Test No. NMX-C-420 ONNCCE(2003)

For Joint Compounds, testing was conducted in accordance with EN 13963.

-   Hardening Time: Paragraph 5.2-   Determination of the absence of fissures: Paragraph 5.3-   Determination of the absence of large particles: Paragraph 5.4-   Determination of adhesion/cohesion: Paragraph 5.5-   Determination of Break Load by Flex: Paragraph 5.8.2

For Exterior Insulation and Finishing Systems (EIFS), testing wasconducted in accordance with ETAG 004.

-   Water Absorption (capillarity test): Section 5.1.3.1-   Freeze-thaw Behavior: Section 5.1.3.2.2-   Resistance to Perforation (Perfotest): Section 5.1.3.3.2-   Base Coat to Insulation Bond Strength: Section 5.1.4.1.1

Example Series 1

In this example, various cementitious tile adhesive compositions wereformulated. Specifically, tile adhesive mortar formulated only with aredispersible polymer was compared to formulations containing aderivatized cellulose, a reactive agent, polyvinyl alcohol polymer, anda vinyl alcohol and vinyl amine copolymer in accordance with the presentdisclosure. After the tile adhesive compositions were formulated, waterwas added and the composition was allowed to harden.

The following table lists the ingredients used to formulate the tileadhesive compositions. Water was added to each example so that all ofthe samples had the same consistency. The produced samples were thentested for various properties as shown in Table 1, below.

TABLE 1 Tile Adhesive Ingredients Control Sample 1-1 Sample 1-2 BaseMortar (Cement/Filler) 97%    97%   97% Cellulose ether-glyoxal product0.24%   0.24% 0.24% Re-dispersible powder 3%   0%   0% Vinyl alcohol andvinyl amine 0% 2.76%   0% copolymer containing 6 mole percent vinylamine* Vinyl alcohol and vinyl amine 0%   0% 2.76% copolymer containing12 mole percent vinyl amine** Water 21%  33.3% 28.6% Open Time (minutes)25 52 22 Tensile Strength @ 5′ minutes 2.4 2.3 2.8 (Nw/mm²) Tensilestrength @ 10′ minutes 2.0 1.5 2.7 (Nw/mm²) Shear resistance (kg/cm²) 2717 21 Compressive Strength (kg/cm²) 40 15 21 *referred to hereinafter asVaVam 6 **referred to hereinafter as VaVam 12

The base mortar contained 80% calcium carbonate and 20% Portland cement.The cement was Portland cement type CPC 30 sold under the tradenameTOLTECA by Cemex. The calcium carbonate was obtained from DerivadosMacroquimicos S. A. de C. V. The cellulose ether/glyoxal product wasobtained from Derivados Macroquimicos S. A. de C. V and had a glyoxalcontent of 0.1:1. The redispersible polymer used in the examples was apolyvinyl acetate ethylene copolymer powder commercially available fromWacker Polymer Systems GmbH under the trade name VINNAPAS 5010. Thepolyvinyl alcohol polymer and the vinyl alcohol and vinyl aminecopolymers were obtained commercially from the Celanese Corporation.

As shown above, incorporating the additive composition of the presentdisclosure into a mortar composition allows for the reduction inredispersible powder without significantly adversely affecting thephysical properties. In fact, Sample 2 showed an increase in tensilestrength over the control. Of particular advantage, incorporation of theadditive composition into Sample 1 dramatically increased the open timeof the formulation.

Although decreases were observed in shear resistance and compressivestrength, it is believed that these decreases are due to the high waterused to achieve uniform mortar consistency.

Example Series 2

In this example, further cementitious compositions were formulated andtested.

The following table lists the ingredients used to formulate the adhesivecompositions. The produced samples were then tested for variousproperties as shown in Table 2, below.

TABLE 2 Tile Adhesive Sample 2-1 Sample 2-2 Sample 2-3 Sample 2-4 Sample2-5 Sample 2-6 Sample 2-7 Cement (%) 14.954 14.9 14.808 14.808 28.12426.634 28.124 Hydroxyl propyl methyl 0.239 0.238 0.237 0.237 0.225 0.2130.225 cellulose (%) PVOH type VaVam 12 VaVam 6 C540S VaVam 6 VaVam 12VaVam 12 C540S PVOH amount (%) 0.06 0.397 0.059 0.059 0.375 0.355 0.375Cross linker Type BORAX BORAX GLYOXAL GLYOXAL BORAX GLYOXAL BORAX Crosslinker amount (%) 0.005 0.03 0.987 0.987 0.028 5.327 0.028 CalciumCarbonate (100 52 52 51 51 54 51 54 mesh) (%) Calcium carbonate (32432.9 32.78 32.577 32.77 16.874 15.98 16.874 mesh) (%) Open time (min) 1930 22 23 23 17 12 Water retention (%) 23.7 26.88 23.14 23.03 24.65 24.7624.85 Adjustability (min) 20 25 17.5 22.5 22.5 22.5 7.5 Open time bytensile 1.38 1.86 0.97 1.26 1.95 1.49 1.72 adhesion strength after 10minutes (Nw/mm²) Tensile adhesion strength 0.65 0.65 0.61 0.71 1.25 1.141.59 after water immersion (Nw/mm²) Tensile adhesion strength 1.82 1.681.55 0.7 2.41 2.03 3.05 after heat aging (Nw/mm²) Compressive strength36 14 18 23 120 122 126 (kg/cm²) Shear adhesion strength 8 8 7 11 27 3220 (kg/cm²) Tile Adhesive Sample 2-8 Sample 2-9 Sample 2-10 Sample 2-11Sample 2-12 Sample 2-13 Sample 2-14 Cement (%) 26.634 28.221 14.9 14.95428.221 14.066 14.9 Hydroxyl propyl methyl 0.213 0.226 0.238 0.239 0.2260.225 0.238 cellulose (%) PVOH type VaVam 6 C540S C540S C540S VaVam 6VaVam 12 VaVam 12 PVOH amount (%) 0.355 0.056 0.397 0.06 0.056 0.3750.397 Cross linker Type GLYOXAL BORAX BORAX BORAX BORAX GLYOXAL BORAXCross linker amount (%) 5.327 0.005 0.03 0.005 0.005 5.626 0.03 CalciumCarbonate 51 55 52 52 55 49 52 (100 mesh) (%) Calcium carbonate 15.9816.932 32.78 32.9 16.932 30.945 32.78 (324 mesh) (%) Open time (min) 2418 10 25 19 15 22 Water retention (%) 26.92 23.74 23.89 23.95 24.4 24.5525 Adjustability (min) 2705 17.5 5 17.5 20 17.5 17.5 Open time bytensile 1.87 1.52 1.24 1.14 1.53 1.4 1.8 adhesion strength after 10minutes (Nw/mm²) Tensile adhesion strength 1.21 1.11 0.64 0.69 1.09 0.780.66 after water immersion Nw/mm²) Tensile adhesion strength 2.23 2.751.17 0.85 1.8 1.23 0.94 after heat aging (Nw/mm²) Compressive strength125 175 37 35 166 29 24 (kg/cm²) Shear adhesion strength 31 30 5 14 5024 18 (kg/cm²) Tile Adhesive Sample 2-15 Sample 2-16 Sample 12-7 Sample2-18 Sample 2-19 Sample 2-20 Sample 2-21 Cement (%) 28.221 26.634 28.12427.959 14.954 14.066 27.959 Hydroxyl propyl ethyl 0.226 0.213 0.2250.224 0.239 0.225 0.224 cellulose (%) PVOH type VaVam 12 C540S VaVam 6VaVam 12 VaVam 6 C540S VaVam 6 PVOH amount (%) 0.056 0.355 0.375 0.0560.06 0.375 0.056 Cross linker Type BORAX GLYOXAL BORAX GLYOXAL BORAXGLYOXAL GLYOXAL Cross linker amount (%) 0.005 5.327 0.028 0.0932 0.0055.626 0.932 Calcium Carbonate (100 55 51 54 54 52 49 54 mesh) (%)Calcium carbonate 16.932 15.98 16.874 16.775 32.9 30.945 16.775 (324mesh) (%) Open time (min) 18 10 30 20 23 12 20 Water retention (%) 23.4323.36 26.21 23.6 24.5 23.9 24.36 Adjustability (min) 20 12.5 22.5 22.517.5 7.5 22.5 Open time by tensile 1.8 1.99 2.82 0.99 1.31 0.91 1.3adhesion strength after 10 minutes (Nw/mm²) Tensile adhesion strength1.24 1.21 1.3 1.4 0.643 0.64 1.05 after water immersion (Nw/mm²) Tensileadhesion 2.23 1.82 2.3 2.95 0.45 0.44 1.99 strength after heat aging(Nw/mm²) Compressive strength 181 166 138 156 20 26 154 (kg/cm²) Shearadhesion strength 46 35 29 28 18 7 26 (kg/cm²) Tile Adhesive Sample 2-22Sample 2-23 Sample 2-24 Cement (%) 27.959 14.808 14.066 Hydroxyl propyl0.224 0.237 0.225 methyl cellulose (%) PVOH type C540S VaVam 12 VaVam 6PVOH amount (%) 0.056 0.059 0.375 Cross linker Type GLYOXAL GLYOXALGLYOXAL Cross linker 0.932 0.987 5.626 amount (%) Calcium Carbonate 5451 49 (100 mesh) (%) Calcium carbonate 16.775 32.577 30.945 (324 mesh)(%) Open time (min) 18 19 32 Water retention (%) 23.44 23.93 27.3Adjustability (min) 17.5 7.5 25 Open time by tensile 1.65 0.66 1.75adhesion strength after 10 minutes (Nw/mm²) Tensile adhesion 1.44 0.620.6 strength after water immersion (Nw/mm²) Tensile adhesion 2.26 0.040.78 strength after heat aging (Nw/mm²) Compressive strength 156 18 19(kg/cm²) Shear adhesion 17 13 5 strength (kg/cm²)

The cement was Portland cement type CPC 30 sold under the tradenameTOLTECA by Cemex. The calcium carbonate was obtained from DerivadosMacroquimicos S. A. de C. V. The cellulose ether/glyoxal product wasobtained from Derivados Macroquimicos S. A. de C. V and had a glyoxalcontent of 0.1:1. The redispersible polymer used in the examples was apolyvinyl acetate ethylene copolymer powder commercially available fromWacker Polymer Systems GmbH under the trade name VINNAPAS 5010. Thepolyvinyl alcohol polymer and the vinyl alcohol and vinyl aminecopolymers were obtained commercially from the Celanese Corporation.

As shown above in the table, the compositions made according to thepresent disclosure exhibited very favorable properties. The table alsoshows that the mortar adhesive attributes can be balanced inside a broadrange of values.

Example Series 3

In this example, further cementitious compositions were formulated andtested.

The following table lists the ingredients used to formulate the adhesivecompositions. The produced samples were then tested for variousproperties as shown in Table 3, below.

TABLE 3 Tile Adhesive Sample Sample Sample Sample Ingredients Control3-1 3-2 3-3 3-4 Cement 28.74% 29.46% 29.51% 24.66% 24.36% Hydroxylpropyl methyl 0.38% 0.39% .39% 0.15% .39% cellulose Re-dispersiblepowder 3.83% 0.98% 0.98% 0.99% 1.95% Copolymer vinyl 0.00% 0.29% 0.10%0.10% 0.10% Alcohol Vinyl Amine Polyvinyl Alcohol 0.00% 0.10% 0.10%0.10% 0.10% Glyoxal/HPMC 0.00% 0.03% 0.05% 0.03% 0.03% Calcium Carbonate67.05% 68.74% 68.86% 73.98% 73.07% pass 325 mesh Open time (min) 43 4644 18 35 Adjustability 45 35 57.5 12.5 17.5 Tensile strength after 1.61.5 1.6 1.3 1.8 5′ minutes (Nw/mm²) Tensile strength after 2.8 2.6 1.81.7 2.3 15′ minutes (Nw/mm²) Tensile Strength after 0.8 0.9 0.8 0.8 0.8water immersion (Nw/mm²) Tensile Strength after 2.0 1.4 1.3 0.9 1.2 heataging (Nw/mm²) Compressive strength 145 112 124 152 111 (kg/cm²) Shearadhesion 36 20 22 32 30 strength (kg/cm²)

The cement was Portland cement type CPC 30 sold under the tradenameTOLTECA by Cemex. The calcium carbonate was obtained from DerivadosMacroquimicos S. A. de C. V. The cellulose ether/glyoxal product wasobtained from Derivados Macroquimicos S. A. de C. V. The redispersiblepolymer used in the examples was a polyvinyl acetate ethylene copolymerpowder commercially available from Wacker Polymer Systems GmbH under thetrade name VINNAPAS 5010. The polyvinyl alcohol polymer and the vinylalcohol and vinyl amine copolymers were obtained commercially from theCelanese Corporation.

As shown in the table above, the samples made according to the presentdisclosure generally exhibited about the same or better properties thanthe Control Sample.

Example Series 4

In this example, further cementitious compositions were formulated andtested.

The following table lists the ingredients used to formulate the adhesivecompositions. The produced samples were then tested for variousproperties as shown in Table 4, below.

TABLE 4 Tile Adhesive Control Sample 4-1 Sample 4-2 Sample 4 -3 Sample4-4 Sample 4-5 Sample 4-6 Cement (%) 28.74 28.68 29.53 29.47 29.53 29.4129.47 Hydroxyl propyl 0.38 0.38 0.39 0.39 0.39 0.39 0.39 methylcellulose (%) Re-dispersible 3.83 3.82 0.98 0.98 0.98 0.98 0.98 powder(%) Copolymer vinyl 0 0.1 0.1 0.29 0.1 0.29 0.1 Alcohol Vinyl Amine (%)PVOH type — 165SF 165SF 165SF C540S C540S 165SF PVOH (%) 0 0.1 0.1 0.10.1 0.29 0.29 Borax (%) 0 0.0019 0.0039 0.0039 0.002 0.002 0.0039Calcium Carbonate (%) 67.05 66.92 68.89 68.76 68.9 68.63 68.76 Open Time38 33 37 35 28 39 26 (min) Open time by tensile 2.07 1.83 1.46 2.02 2.242.32 2.12 adhesion strength after 15 minutes (Nw/mm²) (Adhesion TypeISO-C1) Open time by tensile 2.51 2.32 2.18 2.04 2.57 1.42 2.24 adhesionstrength after 5 minutes (Nw/mm²) (Adhesion Type ISO-C2) Tensileadhesion strength 0.65 1.36 1.16 1.09 1.22 0.75 1.35 after waterimmersion (Nw/mm²) (Adhesion Type ISO-C2) Tensile adhesion strength 1.92.43 2.17 1.95 2.1 1.34 2.26 after heat aging (Nw/mm²) (Adhesion TypeISO-C2) Compressive strength (kg/cm²) 108 116 107 89 94 106 87 Shearadhesion 26 28.28 28.59 27.34 25.68 34.84 29.84 strength (kg/cm²)Tensile adhesion strength 2.18 2.27 2.53 2.36 1.6 2.07 2.46 after 5minutes (Nw/mm²) (Adhesion Type ISO-C2) Tensile adhesion strength — 1.321.18 1.17 1.34 0.84 1.07 after water immersion (Nw/mm²) (Adhesion TypeISO-C2) Tensile adhesion strength 2.43 1.53 1.7 2.21 2.33 1.9 2.22 afterheat aging (Nw/mm²) (Adhesion Type ISO-C1) Tile Adhesive Sample 4-7Sample 4-8 Sample 4-9 Sample 4-10 Sample 4-11 Sample 4-12 Cement (%)29.47 29.47 29.47 29.41 29.41 29.53 Hydroxyl propyl methyl cellulose (%)0.39 0.39 0.39 0.39 0.39 0.39 Re-dispersible powder (%) 0.98 0.98 0.980.98 0.98 0.98 Copolymer vinyl Alcohol Vinyl Amine (%) 0.1 0.29 0.290.29 0.29 0.1 PVOH type C540S C540S C540S 165SF C450S C450S PVOH (%)0.29 0.1 0.1 0.29 0.29 0.1 Borax (%) 0.002 0.0039 0.002 0.002 0.00390.0039 Calcium Carbonate (%) 68.76 68.76 68.76 68.63 68.62 68.89 OpenTime (min) 36 35 33 42 41 42 Open time by tensile adhesion strengthafter 15 2.39 2.64 2.19 2.23 2.34 2.32 minutes (Nw/mm²) (Adhesion TypeISO-C2) Open time by tensile adhesion strength after 5 1.96 2.38 2.182.34 1.99 2.14 minutes (Nw/mm²) (Adhesion Type ISO-C2) Tensile adhesionstrength after water immersion 1.01 0.96 1.34 1.26 0.88 1.27 (Nw/mm²)(Adhesion Type ISO-C2) Tensile adhesion strength after heat aging 1.971.91 2.72 2.11 1.39 1.88 (Nw/mm²) (Adhesion Type ISO-C2) Compressivestrength (kg/cm²) 110 97 101 107 109 93 Shear adhesion strength (kg/cm²)25.48 29.08 32.81 25.62 31.19 25.21 Tensile adhesion strength after 5minutes 2.17 2.35 2.27 2.09 2.03 2.25 (Nw/mm²) (Adhesion Type ISO-C1)Tensile adhesion strength after water immersion 0.92 1.2 1.14 1.28 0.781.35 (Nw/mm²)(Adhesion Type ISO-C1) Tensile adhesion strength after heataging 2.35 2.72 2.13 2.41 2.29 2.28 (Nw/mm²) (Adhesion Type ISO-C1) TileAdhesive Sample 4-13 Sample 4-14 Sample 4-15 Sample 4-16 Sample 4-17Sample 4-18 Cement (%) 29.47 29.47 29.47 29.47 29.41 29.47 Hydroxylpropyl methyl cellulose (%) 0.39 0.39 0.39 0.39 0.39 0.39 Re-dispersiblepowder (%) 0.98 0.98 0.98 0.098 0.98 0.98 Copolymer Vinyl Alcohol VinylAmine (%) 0.29 0.2 0.1 0.1 0.29 0.2 PVOH type 165SF 165SF 165SF C540S165SF C540S PVOH (%) 0.1 0.2 0.29 0.29 0.29 0.2 Borax (%) 0.002 0.00290.002 0.0039 0.0039 0.0029 Calcium Carbonate (%) 68.76 68.76 68.76 68.7668.62 68.76 Open Time (min) 50 37 41 33 38 37 Open time by tensileadhesion strength 2.13 1.87 1.82 2.16 2.54 2.37 after 15 minutes(Nw/mm²) (Adhesion Type ISO-C2) Open time by tensile adhesion strengthafter 2.02 1.61 2.16 1.83 2 1.99 5 minutes (Nw/mm²) (Adhesion TypeISO-C2) Tensile adhesion strength after water immersion 1.23 1.39 1.070.76 1.15 1.22 (Nw/mm²) (Adhesion Type ISO-C2) Tensile adhesion strengthafter heat aging 1.81 2.1 2.03 1.54 1.5 1.9 (Nw/mm²) (Adhesion TypeISO-C2) Compressive strength (kg/cm²) 105 92 88 102 113 126 Shearadhesion strength (kg/cm²) 27.97 29.64 37.33 31.13 37.03 29.1 Tensileadhesion strength after 5 minutes 2.06 1.95 2.25 2.27 2.51 2.44 (Nw/mm²)(Adhesion Type ISO-C1) Tensile adhesion strength after water immersion0.98 1.08 0.93 0.92 1.02 1.07 (Nw/mm²)(Adhesion Type ISO-C1) Tensileadhesion strength after heat 2.18 2.4 1.91 1.91 2 1.9 aging(Nw/mm²)(Adhesion Type ISO-C1)

The cement was Portland cement type CPC 30 sold under the tradenameTOLTECA by Cemex. The calcium carbonate was obtained from DerivadosMacroquimicos S. A. de C. V. The cellulose ether/glyoxal product wasobtained from Derivados Macroquimicos S. A. de C. V and had a glyoxalcontent of 0.1:1. The redispersible polymer used in the examples was apolyvinyl acetate ethylene copolymer powder commercially available fromWacker Polymer Systems GmbH under the trade name VINNAPAS 5010. Thepolyvinyl alcohol polymer and the vinyl alcohol and vinyl aminecopolymers were obtained commercially from the Celanese Corporation.

As shown in the table above, samples made according to the presentdisclosure exhibited very favorable properties in comparison to theControl. Sample Nos. 10 and 11 particularly demonstrated improvedproperties.

Example Series 5 Multifunctional Components

The various components of the inventive compositions can be added asseparate components or combined as a multifunctional component for easeof handling and formulation. One aspect of practicing the presentinvention is to incorporate the nitrogen-containing polymer into aredispersible powder composition as a stabilizer when preparing theredispersible powder emulsion. One might employ, for example, a PVOH-VAMcopolymer, 6 mole % nitrogen as a stabilizer when preparing aredispersible powder emulsion as described in the examples appearingimmediately below.

Polyvinyl acetate based emulsion stabilized with 6 mole % nitrogenPVOH-VAM copolymer:

Equipment:

A 2 liter glass reactor was equipped with a tempered water jacket,mechanical stirrer, feed lines and thermocouple.

Feed Solutions:

Monomers: vinyl acetate (VAM) and optionally vinyl versatate (VeoVa)

-   -   52013-145: 776 g VAM and 258 g VeoVa)    -   52013-149: 775 g VAM and 258 g VeoVa)

Stabilizer Blend

-   -   52013-145: 72 g Celvol 504 Polyvinyl alc.        -   +52 g Vinyl alcohol−vinyl amine copolymer, 12% in water    -   52013-149: 62 g Celvol 504 Polyvinyl alc.        -   +62 g Vinyl alcohol−vinyl amine copolymer, 11% in water

Initiator Potassium persulfate, (PPS) 3.0% w/w inwater)

Buffer: Sodium Acetate 5% w/w in water

Surfactant: Sodium Lauryl Sulfate (SLS) 20% w/w in water

Antifoam: 116 FG (as is) (Harcros)

Redox: Hydrogen peroxide (H2O2)

-   -   Sodium formate salt (SFS)

Sample 5-1 Procedure:

The reactor was charged with

Monomers 119 g Stabilizer blend 915 g Antifoam  0.9 g SLS  9.0 g

The contents were heated to 65° C. with moderate (200 rpm) stirring, andInitiator (19.9 g) added. The temperature is raised and controlled at80° C.

After 10 minutes of stirring, feeds were initiated and maintained.

Monomers 2.25 g/min 300 minutes Initiator: 0.18 g.min 340 minutes

At 300 min, the temperature was raised to 85° C.

The reactor was stirred for an additional 30 minutes, then cooled to 50°C. H2O2 (22.2 g) and SFS (16.0 g) were added to quench thepolymerization and initiator, and the system cooled to 30° C. Theemulsion was spray dried to yield Sample 52013-45.

Sample 5-2 Procedure:

The reactor was charged with

Monomers 119 g Stabilizer blend 930 g Antifoam  0.9 g SLS 6.75 g 

The contents were heated to 65° C. with moderate (200 rpm) stirring, andInitiator (16.6 g) added. The temperature is raised and controlled at80° C.

After 10 minutes of stirring, feeds were initiated and maintained.

Monomers 2.25 g/min 300 minutes Initiator: 0.18 g.min 340 minutes

At 300 min, the temperature was raised to 85° C.

The reactor was stirred for an additional 30 minutes, then cooled to 50°C. H2O2 (22.2 g) and SFS (16.0 g) were added to quench thepolymerization and initatior, and the system cooled to 30° C. Theemulsion was spray dried to yield Sample 52013-149.

The powders prepared had the following assays:

Sample# 5-1 5-2 VAM-VeoVa copolymer 89.3% 89.3% Polyvinyl alcohol 6.2%5.4% Vinyl alcohol-vinyl amine copolymer 4.5% 5.4%

-   -   Experiment 6-21 below used a 1:1 blend of the Sample 5-1        material and the Sample 5-2 material.    -   Experiment 6-22 below used the Sample 5-1 material.

Example Series 6

Following the procedures generally discussed above, a further series ofcompositions was prepared and tested. Details and results appear inTables 5 through 12, below:

TABLE 5 Ingredient Source and Description Ingredient Name CompanyInformation Brief Description Electroland 42.5R Cementos Molins (Spain)42.5R rated Portland Cement Milke 52.5R Heidelberger (Germany) 52.5Rrated Portland Cement H33/H35 Blend Quarzwerke (Germany) 1 Part H33 to 4parts H35 Blend MO 60016P4 SE Tylose (Germany)Hydroxypropylmethylcellulose MOT 60000YP4 SE Tylose (Germany) Solubilitycontrolled Hydroxypropylmethylcellulose MH 60001P4 SE Tylose (Germany)Hydroxyethylmethylcellulose MHS 60000YP4 SE Tylose (Germany) Solubilitycontrolled Hydroxyethylmethylcellulose Culminal 1034 Hercules (US)Hydroxypropylmethylcellulose Culminal 1034R Hercules (US) Solubilitycontrolled Hydroxypropylmethylcellulose Cluminal 8555 Hercules (EU)Hydroxypropylmethylcellulose Demacol 30MN Demacsa (Mexico)Hydroxypropylmethylcellulose Demacol 30MST Demacsa (Mexico) Solubilitycontrolled Hydroxypropylmethylcellulose 5010N Wacker (Germany) VAERedispersible Powder 5012T Wacker (Germany) VAE Redispersible Powder -Thixotropic modification 5044N Wacker (Germany) VAE RedispersiblePowder - Flexible DM117P Elotex VA-VeoVa Redispersible Powder Celvol540S Celanese (US) partially hydrolyzed polyvinylalcohol Celvol 165SFCelanese (US) fully hydrolyzed polyvinylalcohol Berset 2700 Bercin. Inc.(US) cylic amide condensate aqueous blend with glyoxal Polycup 172Hercules (US) aqueous solution of a cationic aminepolymer-epichlorohydrin adduct Zirgel K MEL Chemicals PotassiumZirconium Carbonate SMA 1000P Sartomer (US) Styrene-Malaic Anhydride 1:1molar ratio SMA 3000P Sartomer (US) Styrene-Malaic Anhydride 3:1 molarratio Hyperdrill 247RD QMAX Solutions Inc (US) polyacrylamide PenfordGum 290 Penford (US) Hydroxyethyl ether derivatized corn starch Lupamin9095 BASF Polyvinylamine Lupamin 9030 BASFPolyvinylamine-co-vinylformamide Polyamine B Akzo NobelPolyethyleneamine Glyoxal Sigma-Aldrich (US) 40% aqueous solution ofglyoxal Omyacarb 8-CL Omya Calcium Carbonate Omyacarb 10-BE Omya CalciumCarbonate Caloxol PG Omya Calcium Oxide Glutaraldehyde Sigma-Aldrich(US) Glutaraldehyde Solution Glutaraldehyde Bisulfite Sigma-Aldrich (EU)Glutaraldehyde Salt Boric Acid Sigma-Aldrich (US) Acid Ethyl SuccinateSigma-Aldrich (US) Di-ester

TABLE 6 Sample Compositions Cement Sand Hydroscopic/Rheology ModifierExample Type Amount Type Amount Type Amount 6-1a Proprietary SpanishMortar Producer Blend Demacol 30MST 0.4 6-1b Proprietary Spanish MortarProducer Blend Demacol 30MST 0.4 6-2 Electroland 42.5R 40 QuarzwerkeH33/H35 Blend 60 Tylose MOT 60000YP4 0.4 6-3 Electroland 42.5R 40Quarzwerke H33/H35 Blend 60 Tylose MHS 60000YP4 0.4 6-4 Electroland42.5R 40 Quarzwerke H33/H35 Blend 60 Tylose MOT 60000YP4 0.4 6-5Proprietary Spanish Mortar Producer Blend Demacol 30MST 0.4 6-6Electroland 42.5R 35 Quarzwerke H33/H35 Blend 65 Tylose MHS 60000YP4 0.46-7 Electroland 42.5R 40 Quarzwerke H33/H35 Blend 60 Hyperdrill 247RD0.4 6-8 Electroland 42.5R 40 Quarzwerke H33/H35 Blend 60 Starch PenfordGum 290 0.4 6-9 Proprietary Spanish Mortar Producer Blend Demacol 30MST0.4 6-10 Electroland 42.5R 40 Quarzwerke H33/H35 Blend 60 Tylose MOT60000YP4 0.4 6-11b Electroland 42.5R 40 Quarzwerke H33/H35 Blend 60Tylose MH 60001P4 0.4 6-12a Milke 52.5R 35 Quarzwerke H33/H35 Blend 65Culminal 8555 0.325 6-12b Milke 52.5R 35 Quarzwerke H33/H35 Blend 65Culminal 8555 0.325 6-13 Electroland 42.5R 40 Quarzwerke H33/H35 Blend60 Tylose MO 60016P4 0.4 6-14 Electroland 42.5R 40 Quarzwerke H33/H35Blend 60 Tylose MO 60016P4 0.4 6-15a Electroland 42.5R 40 QuarzwerkeH33/H35 Blend 60 Tylose MO 60016P4 0.4 6-15b Electroland 42.5R 40Quarzwerke H33/H35 Blend 60 Tylose MO 60016P4 0.4 6-16 Milke 52.5R 35Quarzwerke H33/H35 Blend 65 Culminal 8555 0.325 6-17 Milke 52.5R 35Quarzwerke H33/H35 Blend 65 Culminal 8555 0.325 6-20 Electroland 42.5R35 Quarzwerke H33/H35 Blend 65 Demacol 30MN 0.4 6-21 Electroland 42.5R35 Quarzwerke H33/H35 Blend 65 Demacol 30MST 0.4 6-22 Electroland 42.5R35 Quarzwerke H33/H35 Blend 65 Demacol 30MST 0.4 6-23a ProprietarySpanish Mortar Producer Blend Demacol 30MST 0.4 6-23b ProprietarySpanish Mortar Producer Blend Demacol 30MST 0.4 6-23c ProprietarySpanish Mortar Producer Blend Demacol 30MST 0.4 6-24a ProprietarySpanish Mortar Producer Blend Culminal 1034 0.4 6-24b ProprietarySpanish Mortar Producer Blend Culminal 1034R 0.4 6-24c ProprietarySpanish Mortar Producer Blend Culminal 1034R 0.4 6-25a Electroland 42.5R35 Quarzwerke H33/H35 Blend 65 CE Tylose MO 60016P4 0.4 6-25bElectroland 42.5R 35 Quarzwerke H33/H35 Blend 65 CE Tylose MHS 60000YP40.4 6-26a Electroland 42.5R 35 Quarzwerke H33/H35 Blend 65 CE Tylose MH60001P4 0.4 6-26b Electroland 42.5R 50 Quarzwerke H33/H35 Blend 50 CETylose MHS 60000YP4 0.4 Cement Calcium Oxide Sand Hydroscopic/RheologyModifier Example Type Amount Type Amount Type Amount Type Amount 6-18aElectroland 52.5R 25 Caloxol 7.5 Quarzwerke H35 65 CE Tylose MH 15002P60.25 6-18b Electroland 52.5R 25 Caloxol 7.5 Quarzwerke H35 65 CE TyloseMHS 60000YP4 0.25 6-18c Electroland 52.5R 25 Caloxol 7.5 Quarzwerke H3565 CE Tylose MHS 60000YP4 0.25 6-18d Electroland 52.5R 25 Caloxol 7.5Quarzwerke H35 65 CE Tylose MHS 60000YP4 0.25 Cement Calcium OxideCalcium Carbonate Hydroscopic/Rheology Modifier Example Type Amount TypeAmount Type Amount Type Amount 6-19a Electroland 52.5R 19 Caloxol 2Omyacarb Blend** 79 CE Tylose MH 10007P6 0.3 6-19b Electroland 52.5R 19Caloxol 2 Omyacarb Blend** 79 CE Tylose MHS 60000YP4 0.3 6-19cElectroland 52.5R 19 Caloxol 2 Omyacarb Blend** 79 CE Tylose MHS60000YP4 0.3 6-19d Electroland 52.5R 19 Caloxol 2 Omyacarb Blend** 79 CETylose MHS 60000YP4 0.3 Redispersible Powder Nitrogen Containing PolymerPolyvinyl Alcohol Reactive Agent Example Type Amount Type Amount TypeAmount Type Amount 6-1a Wacker 5010N 1 Polyvinylalcohol-co-vinylamine0.4 Celvol 540S 0.2 glyoxal 6-1b Wacker 5010N 1Polyvinylalcohol-co-vinylamine 0.3 Celvol 540S 0.1 glyoxal 6-2 Wacker5010N 2 Lupamin 9095 0.4 Celvol 540S 0.1 glyoxal 6-3 Wacker 5010N 2Lupamin 9030 0.4 Celvol 540S 0.1 glyoxal 6-4 Wacker 5010N 2 Polyamine B0.4 Celvol 540S 0.1 glyoxal 6-5 Wacker 5010N 1Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.2 glyoxal 6-6 Wacker5012T 0.5 Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.2 glyoxal 6-7Wacker 5010N 2 Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.1glyoxal 0.016 6-8 Wacker 5010N 2 Polyvinylalcohol-co-vinylamine 0.4Celvol 540S 0.1 glyoxal 0.016 6-9 Wacker 5010N 1Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.2 glyoxal 6-10 Wacker5010N 2 Polyvinylalcohol-co-vinylamine 0.4 Celvol 0.1 glyoxal 165SF6-11b Wacker 5010N 2 Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.1Berset 2700 0.018 6-12a Wacker 5010N 1 Polyvinylalcohol-co-vinylamine0.3 Celvol 540S 0.1 Glutaraldehyde 0.007 6-12b Wacker 5010N 1Polyvinylalcohol-co-vinylamine 0.3 Celvol 540S 0.1 Glut-Bisulfite 0.00726-13 Wacker 5010N 2 Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.1Polycup 172 0.016 6-14 Wacker 5010N 2 Polyvinylalcohol-co-vinylamine 0.4Celvol 540S 0.1 Zirgel K 0.030 6-15a Wacker 5010N 2Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.1 SMA 1000P 0.028 6-15bWacker 5010N 2 Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.1 SMA3000P 0.083 6-16 Wacker 5010N 1 Polyvinylalcohol-co-vinylamine 0.3Celvol 540S 0.1 E-succinate 0.002 6-17 Wacker 5010N 1Polyvinylalcohol-co-vinylamine 0.3 Celvol 540S 0.1 Boric Acid 0.0026-18a Wacker 5010N 2.0 — — — — — — 6-18b Wacker 5010N 0.5Polyvinylalcohol-co-vinylamine 0.2 C540S 0.05 glyoxal 6-18c Wacker 5010N0.5 Polyvinylalcohol-co-vinylamine 0.25 C540S 0.07 glyoxal 6-18d Wacker5044N 0.5 Polyvinylalcohol-co-vinylamine 0.2 C540S 0.05 glyoxal 6-19aWacker 5010N 1.5 — — — — — — 6-19b Wacker 5010N 0.5Polyvinylalcohol-co-vinylamine 0.2 C540S 0.05 glyoxal 6-19c Wacker 5010N0.5 Polyvinylalcohol-co-vinylamine 0.23 C540S 0.07 glyoxal 6-19d Wacker5044N 0.5 Polyvinylalcohol-co-vinylamine 0.15 C540S 0.05 glyoxal 6-20Wacker 5010N 4 — — — — — 6-21 CZ VA-VeoVa* 4 — — — — glyoxal 6-22 CZVA-VeoVa* 2 Polyvinylalcohol-co-vinylamine 0.146 Celvol 540S 0.13glyoxal 6-23a Wacker 5010N 4 — — — — — — 6-23b Wacker 5010N 1Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.2 glyoxal 6-23c Wacker5010N 1 Polyvinylalcohol-co-vinylamine 0.3 Celvol 540S 0.1 glyoxal 6-24aEloxtex DM117P 4 — — — — — — 6-24b Eloxtex DM117P 1Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.2 glyoxal 6-24c EloxtexDM117P 1 Polyvinylalcohol-co-vinylamine 0.3 Celvol 540S 0.1 glyoxal6-25a Wacker 5012T 4 — — — — — — 6-25b Wacker 5012T 0.5Polyvinylalcohol-co-vinylamine 0.4 Celvol 540S 0.2 glyoxal 6-26a Wacker5044T 4 — — — — — — 6-26b Wacker 5044T 0.5Polyvinylalcohol-co-vinylamine 0.2 Celvol 540S 0.1 glyoxal *CZ VA-VeoVais a RP stabilized with a blend of PVOH andpolyvinylalcohol-co-vinylamine **Omyacarb blend is a 50:50 Blend ofOmyacarb 8 and Omyacarb 10

TABLE 7 Comparison of Compositions with Different Nitrogen-ContainingPolymers Cementitious Tile Adhesive Properties Description of OpenNitrogen % 28 Day Water Heat Freeze- Open Time Time Containing WaterStd. Aging Immersion Aging Thaw 20 min 30 min Slip Flexibility Example #Polymer (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (mm) (mm)6-1a PVOH-VAm 24 2.2 1.2 1.5 1.2 1.2 0.9 6.6 1.7 Copolymer 6-1b PVOH-VAm24 1.0 0.8 1.1 1.5 1.2 0.6 0.1 1.5 Copolymer 6-2 Polyvinylamine 22 1.60.5 0.8 0.6 0.8 0.3 0.3 2.2 Polymer 6-3 Polyvinyl- 21.5 2.0 1.0 1.6 1.31.0 0.5 0.3 2.3 formamide- vinylamine Copolymer 6-4 Polyethyleneimine 231.7 0.8 1.6 0.8 1.3 0.8 1.2 2.0

Table 7 demonstrates the use of a variety of nitrogen containingpolymers in cementitious compositions in a formulation designed for TileAdhesives. Each of the nitrogen containing polymers tested showedpositive results in adhesive properties as well as specialty propertieslike slip resistance, which demonstrates the versatility of thistechnology to work with several different types of nitrogen chemistry.Examples 1-4 also used 2 or less parts of redispersible powder, which isbeneficial to cementitious mortar producers. All results in Table 7 weretested using the EN 12004 Norm.

TABLE 8 Comparison of Compositions with Different Modifiers Descriptionof Cementitious Tile Adhesive Properties Different Rheological Open OpenModifiers and 28 Day Water Heat Freeze- Time Time Hygroscopic % WaterStd. Aging Immersion Aging Thaw 20 min 30 min Slip Flexibility Example #Polymers (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (mm) (mm)6-5 Hydroxypropylmethyl See Example #1 as a reference cellulose 6-6Hydroxyethylmethyl 23 1.7 0.8 1.2 1.3 1.3 0.8 0.2 2.5 cellulose 6-7Polyacrylamide 25 1.1 0.4 1.0 0.8 1.4 0.7 0.1 1.8 6-8 Starch 21 0.3 0.20.1 0.3 0.1 0 0.1 2.0 6-9 Partially Hydrolyzed. See Example #1 as areference High MW PVOH  6-10 Fully Hydrolyzed. 24 1.7 0.7 1.4 1.6 1.51.1 3.2 3.3 High MW PVOH

Table 8 demonstrates the use of a variety of alternate polymericingredients in cementitious compositions in a formulation designed forTile Adhesives. Each example in Table 8 uses the vinylalcohol-vinylaminecopolymer as the nitrogen containing group with glyoxal as the reactiveagent. However, the examples vary in the type of Theological orhygroscopic polymeric modifiers. The technology of the incorporating thenitrogen containing polymer with a reactive agent performs very wellgenerally regardless of what other polymeric additives are used. Twotypes of cellulose derivatives are used with success:hydroxypropyl-methylcellulose and hydroxyethylmethylcellulose. Also, twotypes of polyvinylalcohol are used with success: partially hydrolyzedand fully hydrolyzed. Furthermore, a nitrogen containing Theologicalmodifier like polyacrylamide also showed good properties as a tileadhesive. Starch, on the other hand, clearly imparted poor performanceto the formulation.

TABLE 9 Comparison of Compositions with Different CrosslinkersCementitious Tile Adhesive Properties Open Open 28 Day Water HeatFreeze- Time Time Description of % Water Std. Aging Immersion Aging Thaw20 min 30 min Slip Flexibility Example # Reactive Agents (%)(N/mm{circumflex over ( )}2) (N/mm{circumflex over ( )}2)(N/mm{circumflex over ( )}2) (N/mm{circumflex over ( )}2)(N/mm{circumflex over ( )}2) (N/mm{circumflex over ( )}2) (mm) (mm) 11aDialdehyde #1 - See Examples 1-10 Pure Glyoxal 11b Dialdehyde #2 - 221.7 0.6 1.1 0.8 0.6 0.3 0.3 2.2 Proprietary Glyoxal Blend 12a Dialdehyde#3 - 24.5 1.4 1 1.2 — 0.9 0.3 0.48 1.6 Glutaraldehyde 12b Dialdehyde#4 - 24.5 1.6 1.1 1.2 1.7 1.1 0.6 0.56 1.8 Glutaraldehyde Bisulfite 13Polyamide- 23 2.2 1.1 1.9 1.4 1.1 0.6 0.5 2.1 Epichlorohydrin 14Zirconium Salt 28 1.8 0.6 1.6 1.2 1.6 1.1 8.5 2.1 15a 50:50 SMA Polymer25 1.7 0.7 1.9 0.9 1.1 0.8 1.2 1.9 15b 75:25 SMA Polymer 31 1.5 1.6 1.50.8 1.4 1.3 0.3 3.6 16 Ethyl Succinate 23 1.5 1 1.3 — 1.3 0.7 0.23 1.617 Boric Acid 24 1 1.1 1.3 1.6 0.9 0.6 0.27 1.7

Table 9 demonstrates the use of a variety of reactive agents incementitious compositions in a formulation designed for Tile Adhesiveapplications. Each example in Table 9 uses the vinylalcohol-vinylaminecopolymer as the nitrogen containing group. Despite varying the type ofreactive agent, each example in Table 9 demonstrates a set of qualitytile adhesive with favorable properties. This further supports thetechnology that claims any reactive agent capable of crosslinking withthe nitrogen containing polymer Works in these cementitious systems.

TABLE 10A Comparisons with Difference End Uses (Exterior Insulation andFinishing Systems - EIFS) EIFS Properties - According to ETAG 004 WaterAbsorption Resistance to Base Coat to Insulation Bond AlternativeApplication - Water (6 mm Thickness) Freeze-thaw Perforation Strength(N/mm{circumflex over ( )}2) Exterior Insulation & Demand 1 hour - 24hours - Behavior (Perfotest) Water - 2 Water - 7 Example # FinishingSystems % (kg/m{circumflex over ( )}2) (kg/m{circumflex over ( )}2)(pass/fail) (mm) - Category Dry  hour dry day dry 6-18a Control Sample22 0.14 - pass 0.83 - pass no failures - pass 15 mm (pass) - Cat II 0.160.15 0.17 6-18b Celanese Sample #1 22 0.12 - pass 0.76 - pass nofailures - pass 15 mm (pass) - Cat II 0.15 0.15 0.14 6-18c CelaneseSample #2 22 0.07 - pass 0.53 - pass no failures - pass 12 mm (pass) -Cat II 0.16 0.17 0.17 6-18d Celanese Sample #3 22 0.11 - pass 0.62 -pass no failures - pass 15 mm (pass) - Cat II 0.14 0.15 0.17

Table 10A provides examples of typical formulations used as adhesivesfor Exterior Insulation and Finishing Systems (EIFS). The testingprotocol follows ETAG 004. All samples 18a-18d were mixed to the sameconsistency using 22% water addition by weight. For a sample to pass thewater absorption test, it must have less than 1.0 kg/M² water absorptionafter 1 hour of immersion. All samples pass this test, and all sampleswith the novel nitrogen-containing polymer and reactive agent performbetter than the Control Sample 6-18a with only redispersible powder.Furthermore, if a sample retains less than 0.5 kg/m² water after 24hours of immersion, no Freeze-thaw testing is required. None of thesamples reached the aforementioned benchmark, so all requiredFreeze-thaw testing; however, sample 6. 18c was much improved over thecontrol and came close to the 0.5 kg m² specification, and all CelaneseSamples outperformed the Control. The Freeze-thaw behavior is measuredon a pass fail basis to be determined by the appearance of cracks andfissures. All samples passed the test. Next, all samples received arating of Category II for the perforation test. Category II is themedium tier level for EIFS systems described by light traffic andpotential for impact. Finally, the adhesion of the mortar to theinsulation board was excellent for all samples. In each case, there wascohesive failure within the insulation board and not on the interfacebetween the mortar and insulation. Based on these results, all thesamples with the nitrogen-containing polymer and reactive agentperformed at an identical level in each test to the Control, except forwater absorption, where it was superior.

TABLE 10B Comparisons of Compositions with Different End Uses (JointFiller Compounds) EN 13963 Properties - Jointing for GypsumPlasterboards Fire 315 micron 200 micron Adhesion/ Break Load by %Reaction Curing Crack Course Course Cohesion Flexion Method AlternativeApplication - Water EN13501 Time Test Particles Particles (N/mm2 andFirst Break Example # Joint Filling Compound (%) (rating) (min)(pass/fail) % % Class) Fissure (N) (N) 6-19a Control Sample 35 Not 40 -Short pass 0.08% - pass 0.41% - pass 0.37 - Type C 139 151 Tested 6-19bCelanese Comparison #1 40 A1 50 - Short pass 0.11% - pass 0.32% - pass0.34 - Type C 133 140 6-19c Celanese Comparison #2 35 A1 35 - Short pass0.06% - pass 0.21% - pass 0.37 - Type C 127 132 6-19d CelaneseComparison #3 35 A1 60 - Short pass 0.09% - pass 0.24% - pass 0.33 -Type C 148 157

Table 10B provides examples of typical formulations used as jointingcompound for plasterboards. Formulations 19a-d could be used in Bedding,Finishing, Dual-Purpose, and/or Tapeless Jointing Compounds (Type 1A-4Aand 1B-4B). Example 19a, the control sample, contained a typical amountof redispersible powder for this application, 1.5 PPHC. Each of theCelanese Comparison samples #1-3 which contain a reduced amount ofredispersible powder and the novel nitrogen-containing reactive polymersystem showed highly comparable, mostly identical, results compared tothe control. Furthermore, since examples 19b-d contains less than 1%organic components by weight, they do not require a Fire Reaction testand receive an automatic rating of A1.

TABLE 11 Comparison of Nitrogen Containing Polymer StabilizedRedispersible Powders Cementitious Tile Adhesive Properties 28 Day OpenOpen Description of % Std. Water Heat Freeze- Time Time RedispersibleWater Aging Immersion Aging Thaw 20 min 30 min Slip Flexibility Example# Powder (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (N/mm²) (mm) (mm)6-20 Commercial 21 1.7 0.5 1.6 0.7 0.6 0.3 0.6 2.7 VAE RP 6-21 VA-VeoVA23 1.3 0.4 0.4 1.0 0.2 0.1 0.1 2.0 with PVOH- Vam stabilizer 6-22 Blendof VA- 22 1.1 0.4 0.4 0.9 0.2 0.1 0.1 1.8 VeoVA with PVOH-Vam stabilizer& additional PVOH-Vam

Table 11 is a comparison of a commercially available vinylacetateethylene (VAE) emulsion (Wacker 5010N) in Example 20, with novelCelanese redispersible powders stabilized with a vinylalcohol-vinylaminecopolymer and a reactive agent, glyoxal, in Examples 21 and 22. Example21 is a direct comparison to Example 20, where 4 parts of the VAEredispersible powder were replaced with 4 parts of a VA-VeoVa, nitrogenpolymer stabilized redispersible powder with a reactive agent in thesame general formulation. Example 22 substitutes the VA-VeoVaredispersible powder at a lower addition rate as well as includesadditional vinylalcohol-vinylamine copolymer with a reactive agent.Whereas both Example 21 and 22 have some deficiencies when compared toExample 20, they also showed some novel improvements as well. Forexample, even the with addition of more water in Examples 21 and 22, theslip values of those formulas were far improved over the control inExample 20. This property supports our theory of a crosslinked polymersystem providing specific benefits in cementitious compositions.

One aspect of novelty in this technology is the ability to reduce theoverall level of polymer in a cementitious formulation by reducing thelevel of redispersible powder and still maintaining or even improvingproduct performance. This would represent both a cost savings for mortarformulators and provide them with the ability to make a more balancedformulation. The following Examples 12a-d, demonstrate that novelty.

TABLE 12a Comparison #1 of Invention Compositions with ControlComposition Having Higher Redispersible Powder Content Cementitious TileAdhesive Properties Open % 28 Day Water Heat Freeze- Open Time TimeControl Water Std. Aging Immersion Aging Thaw 20 min 30 min SlipFlexibility Example # Comparison #1 (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²)(N/mm²) (N/mm²) (mm) (mm) 6-23a Control Formulation 24% 2.3 1.0 2.2 2.11.8 1.5 50 2.3 23a 6-23b Celanese 24% 2.2 1.2 1.5 1.2 1.5 0.7 3.0 1.7Comparison 23b 6-23c Celanese 24% 1.0 0.8 1.1 1.5 1.2 0.6 0.1 1.5Comparison 23c

Table 12a compares Control Formulation 23a that contains 4 parts ofWacker 5010N redispersible powder with Examples 23b and 23c that containonly 1 part of Wacker 5010N redispersible powder in typical TileAdhesive based formulations. Example 23b replaces the 3 parts ofredispersible powder with 0.4 parts of vinylalcohol-vinylamine copolymerand 0.2 parts of polyvinylalcohol, and Example 23c uses only 0.3 partsof vinylalcohol-vinylamine copolymer and 0.1 parts of polyvinylalcohol.Example 23b meets all of the same standards (as defined by EN 12004) asthe Control 23a. Example 23b also demonstrates a strong improvement inslip properties as the same water addition rate. Example 23c, which haseven less polymer than 23b, meets the majority of the same standards as23a, only failing to reach 1.0N/mm² in Water Immersion; however, Example23c has extremely high slip resistance that would give it a superiorrating than the control in that category.

TABLE 12b Comparison #2 of Invention Compositions with ControlComposition Having Higher Redispersible Powder Content Cementitious TileAdhesive Properties Open % 28 Day Water Heat Freeze- Open Time TimeControl Comparison Water Std. Aging Immersion Aging Thaw 20 min 30 minSlip Flexibility Example # #2 (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²)(N/mm²) (N/mm²) (mm) (mm) 6-24a Control Formulation 24% 1.8 0.7 1.3 1.81.2 1.0 12.2 2.2 24a 6-24b Celanese 24% 1.1 1.0 0.9 1.2 1.2 0.9 6.6 1.5Comparison 24b 6-24c Celanese 24% 2.0 0.6 0.8 2.0 1.1 0.8 0.8 1.6Comparison 24c

Table 12b compares Control Formulation 24a that contains 4 parts ofElotex DM117P redispersible powder with Examples 24b and 24c thatcontain only 1 part of Elotex DM117P redispersible powder in typicalTile Adhesive based formulations. Example 24b replaces the 3 parts ofredispersible powder with 0.4 parts of vinylalcohol-vinylamine copolymerand 0.2 parts of polyvinylalcohol, and Example 24c uses only 0.3 partsof vinylalcohol-vinylamine copolymer and 0.1 parts of polyvinylalcohol.Both Examples 24b and 24c meet the exact same standards (as defined byEN 12004) as the Control 24a sample. Also, both Celanese Comparisonsamples show a strong improvement in slip with the same level of wateraddition.

TABLE 12c Comparison #3 of Invention Compositions with ControlComposition Having Higher Redispersible Powder Content Cementitious TileAdhesive Properties Open % 28 Day Water Heat Freeze- Open Time TimeControl Comparison Water Std. Aging Immersion Aging Thaw 20 min 30 minSlip Flexibility Example # #3 (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²)(N/mm²) (N/mm²) (mm) (mm) 6-25a Control Formulation 22% 1.4 0.7 1.3 1.60.7 0.3 0.3 3.1 25a 6-25b Celanese 23% 1.7 0.8 1.2 1.3 1.3 0.8 0.2 2.5Comparison 24b

Table 12c compares Control Formulation 25a that contains 4 parts ofWacker 5012T redispersible powder with Examples 25b that contains only0.5 parts of Wacker 5012T redispersible powder in typical Tile Adhesivebased formulations. Example 25b replaces the 3.5 parts of redispersiblepowder with 0.4 parts of vinylalcohol-vinylamine copolymer and 0.2 partsof polyvinylalcohol. Despite removing the majority of the redispersiblepowder, Sample 25b has the same rating (based on EN 12004) as theControl 25a. Furthermore, Sample 25b shows better 28 Day again, WaterImmersion, Open Time, and Slip performance.

TABLE 12d Comparison #3 of Invention Compositions with ControlComposition Having Higher Redispersible Powder Content Cementitious TileAdhesive Properties Open % 28 Day Water Heat Freeze- Open Time TimeControl Water Std. Aging Immersion Aging Thaw 20 min 30 min SlipFlexibility Example # Comparison #4 (%) (N/mm²) (N/mm²) (N/mm²) (N/mm²)(N/mm²) (N/mm²) (mm) (mm) 6-26a Control Formulation 22% 1.2 0.9 1.3 1.71.2 0.8 4.7 2.4 25a 6-26b Celanese 26% 1.5 1.2 1.0 1.4 0.9 0.6 6.6 1.8Comparison 26b

Table 12d compares Control Formulation 26a that contains 4 parts ofWacker 5044N redispersible powder with Examples 26b that contains only0.5 parts of Wacker 5044N redispersible powder in typical Tile Adhesivebased formulations. Example 26b replaces the 3.5 parts of redispersiblepowder with only 0.2 parts of vinylalcohol-vinylamine copolymer and 0.1parts of polyvinylalcohol. Despite removing the majority of theredispersible powder, Sample 26b has a better rating (based on EN 12004)than the Control 26a because Sample 26b provides a higher level ofperformance.

It is appreciated from the foregoing examples that cementitiouscompositions in accordance with the invention exhibit a superior balanceof properties, including flexibility, open times and so forth even withlow levels of polymer additive. For example, the invention compositionsin the adhesive exhibit surprising slip and water resistance which is ahighly desirable feature for these classes of compositions.

There is thus provided in accordance with the invention the improvementfor cementitious compositions comprising a reactive polymericcomposition including a nitrogen-containing polymer and a reactive agentcapable of crosslinking with the nitrogen of the polymer in situ withinthe cementitious composition. In some cases, the nitrogen-containingpolymer composition comprises an amine-functional polymer, while inothers, the nitrogen-containing polymer comprises an amide-functionalpolymer.

A suitable polymer is a vinyl alcohol and vinyl amine copolymer whichcontains from 2 mole percent to 30 mole percent vinyl amine, such asfrom 2 mole percent to 12 mole percent vinyl amine. Another suitablepolymer is a vinyl amine homopolymer. Still other suitablenitrogen-containing polymers are vinylformamide-vinylamine copolymersand ethyleneimine polymers. Typically, the nitrogen-containing polymeris present in the cementitious composition in an amount of from 0.01% to5% based on the dry weight of the cementitious composition such as wherethe nitrogen-containing polymer is present in the cementitiouscomposition in an amount of from 0.1% to 2% based on the dry weight ofthe cementitious composition.

The reactive agent may comprise polyaldehydes, dialdehydes such asglyoxal; dicarboxylic anhydrides, maleic anhydride copolymers such asstyrene maleic anhydride copolymer; an epichlorohydrin resin; polyacids,such as polyacrylic acid or polymethacrylic acid; polyacid esters suchas polymethacrylate and polymethylmethacrylate; polyvinyl alcohol esterssuch as polyvinyl alcohol-acetoacetic acid ester (Gohsifimer Z); or azirconium salt. Suitable reactive agents thus include a gluteraldehyde;a succinic dialdehyde; a blocked glyoxal; a cationic amineepichlorohydrin polymer; an amide-epichlorohydrin polymer; a potassiumzirconium carbonate; an ammonium zirconium carbonate; a ketoneformaldehyde; a styrene maleic anhydride copolymer; or a cyclic amidecondensate. The dry weight ratio of reactive agent:nitrogen-containingpolymer in the reactive polymeric composition is generally from 0.01 to0.3; typically from 0.025 to 0.1. So also, the molar equivalent ratio ofthe reactive moieties of the reactive agent to nitrogen in thenitrogen-containing polymer is generally from 1:1 to 1:500; typicallythe molar equivalent ratio of the reactive moieties of the reactiveagent to nitrogen in the nitrogen-containing polymer is from 1:10 to1:200; and preferably the molar equivalent ratio of the reactivemoieties of the reactive agent to nitrogen in the nitrogen-containingpolymer is from 1:25 to 1:75.

In one preferred aspect, the reactive agent is reversibly reacted with acarrier prior to being provided to the reactive polymeric composition.The carrier may be a cellulose derivative, polyvinyl alcohol, or aninorganic carrier selected from clays, calcium carbonate and calciumoxide. The dry weight ratio of reactive agent:carrier is generally from0.001:1 to 0.5:1; typically dry weight ratio of reactive agent:carrieris from 0.01:1 to 0.1:1. Suitable cellulose derivatives arehydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose. Stillothers which may be employed include methyl cellulose; hydroxyethylcellulose; hydroxypropyl cellulose; carboxymethyl cellulose;hydroxyethyl cellulose; ethyl hydroxyethyl cellulose; ethyl cellulose ormixtures thereof. In general, dry weight ratio of thenitrogen-containing polymer to the cellulose derivative is from 1:5 to5:1; such as where the dry weight ratio of the nitrogen-containingpolymer to the cellulose derivative is from 1:4 to 4:1; or where the dryweight ratio of the nitrogen-containing polymer to the cellulosederivative is from 1:2 to 2:1.

In many cases, the reactive polymeric composition comprises a vinylalcohol polymer or copolymer thereof as well as a cellulose derivatewhere the dry weight ratio of the cellulose derivative to the vinylalcohol polymer is from 5:1 to 1:5. Typically in such cases the dryweight ratio of the cellulose derivative to the vinyl alcohol polymer isfrom 1:4 to 4:1 or from 1:1 to 3:1.

Generally speaking, when polyvinyl alcohol or vinyl alcohol copolymersare used, the vinyl alcohol polymer is present in an amount of from0.05% to 1% based on the dry weight of the cementitious composition andthe reactive polymeric composition is present in the cementitiouscomposition in an amount of from 0.1% to 15% based on the dry weight ofthe cementitious composition. Perhaps more preferably, the reactivepolymeric composition is present in the cementitious composition in anamount of from 0.25% to 5% based on the dry weight of the cementitiouscomposition. In some preferred cases, the reactive polymeric compositionis present in the cementitious composition in an amount of from 0.5% to2% based on the dry weight of the cementitious composition.

The cementitious compositions of this invention are especially useful inconnection with tile adhesive compositions, exterior insulationfinishing compositions, joint filler compositions, as well as all cementcompositions which traditionally employ redispersible powders such astroweling compositions; thin bed mortar compositions; sealing slurrycompositions; powder paint compositions; rendering plaster compositions;patch and repair mortar compositions; mineral plaster compositions;gypsum compositions; grout compositions; facade coating compositions;concrete repair compositions; coatings; or self-leveling compositions.

In various applications, the reactive polymeric composition is admixeddry with the other components of the cementitious composition which arelikewise dry, while in other cases the reactive polymeric composition isadmixed wet or dry with a wet cementitious composition if so desired. Instill yet further applications of the inventive compositions, thereactive polymeric composition is admixed wet with the other componentsof the cementitious composition, where the other components are wet ordry.

In another aspect of the invention, three is provided a cementitiouscomposition comprising an inorganic binder; an inorganic filler; apolymeric composition including a nitrogen-containing polymer and areactive agent capable of crosslinking with the nitrogen of the polymerin situ within the cementitious composition; and a cellulose derivativeor a vinyl alcohol polymer which is also reactive with the reactiveagent. Generally, the inorganic binder comprises cement, gypsum, analuminate or mixtures thereof, whereas the filler comprises calciumcarbonate, quartz, or mixtures thereof.

The compositions may further include an additive, the additivecomprising a lubricant, hydrophobic agent fibers, pigments or mixturesthereof. Generally, the binder is present in an amount from 20 parts to50 parts per hundred dry weight cement (PPHC), the filler is present inan amount from 10 parts to 90 PPHC and the nitrogen-containing polymeris present in an amount from 0.01 to 2 PPHC. A cellulose derivative maybe present in an amount of from 0.01 to 3 PPHC and the compositionfurther comprises a polyvinyl alcohol polymer in an amount of from 0.01to 2 PPHC. In some embodiments, the composition containsa redispersiblepolymer powder, the redispersible polymer powder being present in anamount from 0.1 to 15 PPHC. The redispersible polymer powder may bepresent in an amount from 0.2 to 8 PPHC or from 0.25 to 5 PPHC or in anamount greater than 0.2 and less than 2 PPHC. Other suitable amounts forredispersible powder is present is from 0.1 to 8 PPHC; less than 4 PPHC;less than 3 PPHC; or less than 2 PPHC.

In still another aspect of the nvnetion there is provided an additivecomposition for mixing into a cementitious blend including an inorganicbinder and an inorganic filler, the additive composition including areactive polymeric composition comprising a nitrogen-containing polymerand a reactive agent capable of crosslinking with the nitrogen of thepolymer in situ within the cementitious blend; and wherein the reactiveagent is also reactive with cellulose derivatives and vinyl alcoholpolymers. The reactive agent suitably comprises a gluteraldehyde; asuccinic dialdehyde; a blocked glyoxal; a cationic amine epichlorohydrinpolymer; an amide-epichlorohydrin polymer; a potassium zirconiumcarbonate; an ammonium zirconium carbonate; a ketone formaldehyde; astyrene maleic anhydride copolymer; or a cyclic amide condensate.

In yet a further aspect of the invention, there is provided an additivecomposition for mixing into a cementitious blend including an inorganicbinder, an inorganic filler, the additive composition including aredispersible emulsion polymer composition as well as anitrogen-containing additive polymer and a reactive agent capable ofreacting with the nitrogen of the additive polymer in situ within thecementitious blend; and wherein the reactive agent is also reactive withcellulose derivatives and vinyl alcohol polymers. The redispersibleemulsion polymer composition generally includes an emulsion polymerformed from one or more unbranched alkylcarboxylic acid vinyl estermonomers, branched alkylcarboxylic acid vinyl ester monomers, alcoholmethacrylic acid ester monomers, vinyl aromatic monomers, olefinmonomers, diene monomers, or vinyl halide monomers. A typical emulsionpolymer comprises a copolymer of vinyl acetate and ethylene. Anothersuitable emulsion polymer comprises a copolymer of vinyl acetate and avinyl ester of a versatic acid. Generally, the nitrogen-containingadditive polymer is present in the additive composition in an amountfrom 4% to 20% by dry weight and the redispersible powder is present inan amount of from 1% to 15% based on the dry weight of the cementitiousblend and the additive composition mixed therewith. The redispersiblepowder may be present in an amount of less than 8% based on the dryweight of the cementitious blend and the additive composition mixedtherewith or the redispersible powder is present in an amount of lessthan 5% based on the dry weight of the cementitious blend and theadditive composition mixed therewith. In some preferred cases, theredispersible powder is present in an amount of less than 2% based onthe dry weight of the cementitious blend and the additive compositionmixed therewith.

While the invention has been described in detail, modifications withinthe spirit and scope of the invention will be readily apparent to thoseof skill in the art. In view of the foregoing discussion, relevantknowledge in the art and references discussed above in connection withthe Background and Detailed Description, the disclosures of which areall incorporated herein by reference, further description is deemedunnecessary. In addition, it should be understood that aspects of thevarious embodiments may be interchanged either in whole or in part.Furthermore, those of ordinary skill in the art will appreciate that theforegoing description is by way of example only, and is not intended tolimit the invention as further described in the appended claims.

1. In a cementitious composition of the class including an inorganicbinder and a filler, the improvement comprising a reactive polymericcomposition including a nitrogen-containing polymer and a reactive agentcapable of crosslinking with the nitrogen of the polymer in situ withinthe cementitious composition, wherein the reactive agent is selectedfrom polyaldehydes, polyaldehyde salts, dicarboxylic anhydrides, maleicanyhydride copolymers, epichlorohydrin resins, zirconium salts, boricacid and mixtures thereof.
 2. The improvement according to claim 1,wherein the nitrogen-containing polymer is a vinyl alcohol and vinylamine copolymer.
 3. The improvement according to claim 1, wherein thenitrogen-containing polymer contains from 2 mole percent to 30 molepercent vinyl amine.
 4. The improvement according to claim 1, whereinthe nitrogen-containing polymer contains from 2 mole percent to 12 molepercent vinyl amine.
 5. The improvement according to claim 1, whereinthe nitrogen-containing polymer is a vinyl amine homopolymer.
 6. Theimprovement according to claim 1, wherein the nitrogen-containingpolymer is a vinylformamide-vinylamine copolymer.
 7. The improvementaccording to claim 1, wherein the reactive agent comprisesglutaraldehyde.
 8. The improvement according to claim 1, wherein thereactive agent comprises a glutaraldehyde bisulfite.
 9. The improvementaccording to claim 1, wherein the reactive agent comprises ethylsuccinate.
 10. The improvement according to claim 1, wherein thereactive agent comprises boric acid.
 11. The improvement according toclaim 1, wherein the reactive agent comprises a succinic dialdehyde; adialdehyde salt; a blocked glyoxal; a cationic amine epichlorohydrinpolymer; an amide-epichlorohydrin polymer; a potassium zirconiumcarbonate; an ammonium zirconium carbonate; a ketone formaldehyde; astyrene maleic anhydride copolymer; a cyclic amide condensate; apolyacid; a polyacrylic acid selected from polyacrylic acid andpolymethacrylic acid; a polyacid ester; a di-ester; a polyacid esterselected from polymeth-acrylate and polymethylmethacrylate; a polyvinylalcohol ester; or a polyvinyl alcohol-acetoacetic acid ester.
 12. Anadditive composition for mixing into a cementitious blend including aninorganic binder and an inorganic filler, the additive compositionincluding a reactive polymeric composition comprising anitrogen-containing polymer and a reactive agent capable of crosslinkingwith the nitrogen of the polymer in situ within the cementitious blend;and wherein the reactive agent is also the reactive with cellulosederivatives and vinyl alcohol polymers, and wherein the reactive agentis selected from polyaldehydes, polyaldehyde salts, dicarboxylicanhydrides, maleic anyhydride copolymers, epichlorohydrin resins,zirconium salts, boric acid and mixtures thereof.
 13. The additivecomposition according to claim 12, wherein the reactive agent comprisesglutaraldehyde.
 14. The additive composition according to claim 12,wherein the reactive agent comprises a glutaraldehyde bisulfite.
 15. Theadditive composition according to claim 12, wherein the reactive agentcomprises ethyl succinate.
 16. The additive composition according toclaim 12, wherein the reactive agent comprises boric acid.
 17. Theadditive composition according to claim 12, wherein the reactive agentcomprises a succinic dialdehyde; a dialdehyde salt; a blocked glyoxal; acationic amine epichlorohydrin polymer; an amide-epichlorohydrinpolymer; a potassium zirconium carbonate; an ammonium zirconiumcarbonate; a ketone formaldehyde; a styrene maleic anhydride copolymer;a cyclic amide condensate; a polyacid; a polyacrylic acid selected frompolyacrylic acid and polymethacrylic acid; a polyacid ester; a di-ester;a polyacid ester selected from polymeth-acrylate andpolymethylmethacrylate; a polyvinyl alcohol ester; or a polyvinylalcohol-acetoacetic acid ester.
 18. The additive composition accordingto claim 12, wherein the nitrogen-containing polymer compositioncomprises an amine-functional polymer.
 19. The additive compositionaccording to claim 12, wherein the nitrogen-containing polymer is avinyl alcohol and vinyl amine copolymer.
 20. An additive composition formixing into a cementitious blend including an inorganic binder, aninorganic filler, the additive composition including a redispersibleemulsion polymer composition comprising an emulsion polymer stabilizedwith a nitrogen-containing stabilizing polymer and a reactive agentcapable of crosslinking with the nitrogen of the stabilizing polymer insitu within the cementitious blend; and wherein the reactive agent isalso reactive with cellulose derivatives and vinyl alcohol polymers, andwherein the reactive agent is selected from polyaldehydes, polyaldehydesalts, dicarboxylic anhydrides, maleic anyhydride copolymers,epichlorohydrin resins, zirconium salts, boric acid and mixturesthereof.